A fracture mechanics study of the phase separating planar electrodes: Phase field modeling and analytical results

NASA Astrophysics Data System (ADS)

Haftbaradaran, H.; Maddahian, A.; Mossaiby, F.

2017-05-01

It is well known that phase separation could severely intensify mechanical degradation and expedite capacity fading in lithium-ion battery electrodes during electrochemical cycling. Experiments have frequently revealed that such degradation effects could be substantially mitigated via reducing the electrode feature size to the nanoscale. The purpose of this work is to present a fracture mechanics study of the phase separating planar electrodes. To this end, a phase field model is utilized to predict how phase separation affects evolution of the solute distribution and stress profile in a planar electrode. Behavior of the preexisting flaws in the electrode in response to the diffusion induced stresses is then examined via computing the time dependent stress intensity factor arising at the tip of flaws during both the insertion and extraction half-cycles. Further, adopting a sharp-interphase approximation of the system, a critical electrode thickness is derived below which the phase separating electrode becomes flaw tolerant. Numerical results of the phase field model are also compared against analytical predictions of the sharp-interphase model. The results are further discussed with reference to the available experiments in the literature. Finally, some of the limitations of the model are cautioned.

On the effect of basic and acidic additives on the separation of the enantiomers of some basic drugs with polysaccharide-based chiral selectors and polar organic mobile phases.

PubMed

Mosiashvili, L; Chankvetadze, L; Farkas, T; Chankvetadze, B

2013-11-22

This article reports the systematic study of the effect of basic and acidic additives on HPLC separation of enantiomers of some basic chiral drugs on polysaccharide-based chiral columns under polar organic mobile-phase conditions. In contrary to generally accepted opinion that the basic additives improve the separation of enantiomers of basic compounds, the multiple scenarios were observed including the increase, decrease, disappearance and appearance of separation, as well as the reversal of the enantiomer elution order of studied basic compounds induced by the acidic additives. These effects were observed on most of the studied 6 chiral columns in 2-propanol and acetonitrile as mobile phases and diethylamine as a basic additive. As acidic additives formic acid was used systematically and acetic acid and trifluoroacetic acid were applied for comparative purposes. This study illustrates that the minor acidic additives to the mobile phase can be used as for the adjustment of separation selectivity and the enantiomer elution order of basic compounds, as well as for study of chiral recognition mechanisms with polysaccharide-based chiral stationary phases. Copyright © 2013 Elsevier B.V. All rights reserved.

Vapor-liquid phase separator studies

NASA Technical Reports Server (NTRS)

Yuan, S. W. K.; Lee, J. M.; Kim, Y. I.; Hepler, W. A.; Frederking, T. H. K.

1983-01-01

Porous plugs serve as both entropy rejection devices and phase separation components separating the vapor phase on the downstream side from liquid Helium 2 upstream. The liquid upstream is the cryo-reservoir fluid needed for equipment cooling by means of Helium 2, i.e Helium-4 below its lambda temperature in near-saturated states. The topics outlined are characteristic lengths, transport equations and plug results.

Development of a novel amide-silica stationary phase for the reversed-phase HPLC separation of different classes of phytohormones.

PubMed

Aral, Hayriye; Aral, Tarık; Ziyadanoğulları, Berrin; Ziyadanoğulları, Recep

2013-11-15

A novel amide-bonded silica stationary phase was prepared starting from N-Boc-phenylalanine, cyclohexylamine and spherical silica gel (4 µm, 60 Å). The amide ligand was synthesised with high yield. The resulting amide bonded stationary phase was characterised by SEM, IR and elemental analysis. The resulting selector bearing a polar amide group is used for the reversed-phase chromatography separation of different classes of thirteen phytohormones (plant hormones). The chromatographic behaviours of these analytes on the amide-silica stationary phase were compared with those of RP-C18 column under same conditions. The effects of different separation conditions, such as mobile phase, pH value, flow rate and temperature, on the separation and retention behaviours of the 13 phytohormones in this system were studied. The optimum separation was achieved using reversed-phase HPLC gradient elution with an aqueous mobile phase containing pH=6.85 potassium phosphate buffer (20 mM) and acetonitrile with a 22 °C column temperature. Under these experimental conditions, the 12 phytohormones could be separated and detected at 230 or 270 nm within 26 min. Copyright © 2013 Elsevier B.V. All rights reserved.

Sequence control of phase separation and dewetting in PS/PVME blend thin films by changing molecular weight of PS.

PubMed

Xia, Tian; Qin, Yaping; Huang, Yajiang; Huang, Ting; Xu, Jianhui; Li, Youbing

2016-11-28

The morphology evolution mechanism of polystyrene (PS)/poly (vinyl methyl ether) (PVME) blend thin films with different PS molecular weights (M w ) was studied. It was found that the morphology evolution was closely related to the molecular weight asymmetry between PS and PVME. In the film where M w (PS) ≈ M w (PVME), dewetting happened at the interface between the bottom layer and substrate after SD phase separation. While in the film where M w (PS) > M w (PVME), dewetting happened at the interface between the middle PS/PVME blend layer and bottom PVME layer near the substrate prior to phase separation. The different sequences of phase separation and dewetting and different interface for dewetting occurrence were studied by regarding the competitive effects of viscoelasticity contrast between polymer components and preferential wetting between PVME and the substrate. The viscoelastic nature of the PS component played a crucial role in the sequence of phase separation and dewetting.

Ordering-separation phase transitions in a Co3V alloy

NASA Astrophysics Data System (ADS)

Ustinovshchikov, Yu. I.

2017-01-01

The microstructure of the Co3V alloy formed by heat treatment at various temperatures is studied by transmission electron microscopy. Two ordering-separation phase transitions are revealed at temperatures of 400-450 and 800°C. At the high-temperature phase separation, the microstructure consists of bcc vanadium particles and an fcc solid solution; at the low-temperature phase separation, the microstructure is cellular. In the ordering range, the microstructure consists of chemical compound Co3V particles chaotically arranged in the solid solution. The structure of the Co3V alloy is shown not to correspond to the structures indicated in the Co-V phase diagram at any temperatures.

Conserved interdomain linker promotes phase separation of the multivalent adaptor protein Nck

PubMed Central

Banjade, Sudeep; Wu, Qiong; Mittal, Anuradha; Peeples, William B.; Pappu, Rohit V.; Rosen, Michael K.

2015-01-01

The organization of membranes, the cytosol, and the nucleus of eukaryotic cells can be controlled through phase separation of lipids, proteins, and nucleic acids. Collective interactions of multivalent molecules mediated by modular binding domains can induce gelation and phase separation in several cytosolic and membrane-associated systems. The adaptor protein Nck has three SRC-homology 3 (SH3) domains that bind multiple proline-rich segments in the actin regulatory protein neuronal Wiskott-Aldrich syndrome protein (N-WASP) and an SH2 domain that binds to multiple phosphotyrosine sites in the adhesion protein nephrin, leading to phase separation. Here, we show that the 50-residue linker between the first two SH3 domains of Nck enhances phase separation of Nck/N-WASP/nephrin assemblies. Two linear motifs within this element, as well as its overall positively charged character, are important for this effect. The linker increases the driving force for self-assembly of Nck, likely through weak interactions with the second SH3 domain, and this effect appears to promote phase separation. The linker sequence is highly conserved, suggesting that the sequence determinants of the driving forces for phase separation may be generally important to Nck functions. Our studies demonstrate that linker regions between modular domains can contribute to the driving forces for self-assembly and phase separation of multivalent proteins. PMID:26553976

Observations of liquid-liquid phase separation in several types of secondary organic materials free of inorganic salts

NASA Astrophysics Data System (ADS)

Song, M.; Liu, P.; Martin, S. T.; Bertram, A. K.; Ham, S.

2016-12-01

Particles consisting of secondary organic materials (SOMs) are ubiquitous in the atmosphere. In order to predict the role of these particles in climate, visibility, and atmospheric chemistry, knowledge of the phase states of the particles is required. However, the phase states of the SOMs are still poorly understood. Herein we focused on liquid-liquid phase separation in different types of SOM particles free of inorganic salts produced by the ozonolysis of β-caryophyllene, ozonolysis of limonene, photo-oxidation of isoprene, and photo-oxidation of toluene. Liquid-liquid phase separation was investigated using optical microscopy and SOM particle mass concentrations ranging from 15 µg·m-3 to 7000 µg·m-3. During humidity cycles, liquid-liquid phase separation was observed in β-caryophyllene-derived SOM and limonene-derived SOM particles while no liquid-liquid phase separation was observed in isoprene-derived SOM and toluene-derived SOM particles. Results from the studies will be presented.

Numerical analysis of wet separation of particles by density differences

NASA Astrophysics Data System (ADS)

Markauskas, D.; Kruggel-Emden, H.

2017-07-01

Wet particle separation is widely used in mineral processing and plastic recycling to separate mixtures of particulate materials into further usable fractions due to density differences. This work presents efforts aiming to numerically analyze the wet separation of particles with different densities. In the current study the discrete element method (DEM) is used for the solid phase while the smoothed particle hydrodynamics (SPH) is used for modeling of the liquid phase. The two phases are coupled by the use of a volume averaging technique. In the current study, simulations of spherical particle separation were performed. In these simulations, a set of generated particles with two different densities is dropped into a rectangular container filled with liquid. The results of simulations with two different mixtures of particles demonstrated how separation depends on the densities of particles.

Integral equation theory study on the phase separation in star polymer nanocomposite melts.

PubMed

Zhao, Lei; Li, Yi-Gui; Zhong, Chongli

2007-10-21

The polymer reference interaction site model theory is used to investigate phase separation in star polymer nanocomposite melts. Two kinds of spinodal curves were obtained: classic fluid phase boundary for relatively low nanoparticle-monomer attraction strength and network phase boundary for relatively high nanoparticle-monomer attraction strength. The network phase boundaries are much more sensitive with nanoparticle-monomer attraction strength than the fluid phase boundaries. The interference among the arm number, arm length, and nanoparticle-monomer attraction strength was systematically investigated. When the arm lengths are short, the network phase boundary shows a marked shift toward less miscibility with increasing arm number. When the arm lengths are long enough, the network phase boundaries show opposite trends. There exists a crossover arm number value for star polymer nanocomposite melts, below which the network phase separation is consistent with that of chain polymer nanocomposite melts. However, the network phase separation shows qualitatively different behaviors when the arm number is larger than this value.

Polymerization- and Solvent-Induced Phase Separation in Hydrophilic-rich Dentin Adhesive Mimic

PubMed Central

Abedin, Farhana; Ye, Qiang; Good, Holly J; Parthasarathy, Ranganathan; Spencer, Paulette

2014-01-01

Current dental resin undergoes phase separation into hydrophobic-rich and hydrophilic-rich phases during infiltration of the over-wet demineralized collagen matrix. Such phase separation undermines the integrity and durability of the bond at the composite/tooth interface. This study marks the first time that the polymerization kinetics of model hydrophilic-rich phase of dental adhesive has been determined. Samples were prepared by adding varying water content to neat resins made from 95 and 99wt% hydroxyethylmethacrylate (HEMA) and 5 and 1wt% (2,2-bis[4-(2-hydroxy-3-methacryloxypropoxy)phenyl1]-propane (BisGMA) prior to light curing. Viscosity of the formulations decreased with increased water content. The photo-polymerization kinetics study was carried out by time-resolved FTIR spectrum collector. All of the samples exhibited two-stage polymerization behavior which has not been reported previously for dental resin formulation. The lowest secondary rate maxima were observed for water content of 10-30%wt. Differential scanning calorimetry (DSC) showed two glass transition temperatures for the hydrophilic-rich phase of dental adhesive. The DSC results indicate that the heterogeneity within the final polymer structure decreased with increased water content. The results suggest a reaction mechanism involving both polymerization-induced phase separation (PIPs) and solvent-induced phase separation (SIPs) for the model hydrophilic-rich phase of dental resin. PMID:24631658

Dynamics of polymerization induced phase separation in reactive polymer blends

NASA Astrophysics Data System (ADS)

Lee, Jaehyung

Mechanisms and dynamics of phase decomposition following polymerization induced phase separation (PIPS) of reactive polymer blends have been investigated experimentally and theoretically. The phenomenon of PIPS is a non-equilibrium and non-linear dynamic process. The mechanism of PIPS has been thought to be a nucleation and growth (NG) type originally, however, newer results indicate spinodal decomposition (SD). In PIPS, the coexistence curve generally passes through the reaction temperature at off-critical compositions, thus phase separation has to be initiated first in the metastable region where nucleation occurs. When the system farther drifts from the metastable to unstable region, the NG structure transforms to the SD bicontinuous morphology. The crossover behavior of PIPS may be called nucleation initiated spinodal decomposition (NISD). The formation of newer domains between the existing ones is responsible for the early stage of PIPS. Since PIPS is non- equilibrium kinetic process, it would not be surprising to discern either or both structures. The phase separation dynamics of DGEBA/CTBN mixtures having various kinds of curing agents from low reactivity to high reactivity and various amount of curing agents were examined at various reaction temperatures. The phase separation behavior was monitored by a quantity of scattered light intensity experimentally and by a quantity of collective structure factor numerically. Prior to the study of phase separation dynamics, a preliminary investigation on the isothermal cure behavior of the mixtures were executed in order to determine reaction kinetics parameters. The cure behavior followed the overall second order reaction kinetics. Next, based on the knowledge obtained from the phase separation dynamics study of DGEBA/CTBN mixtures, the phase separation dynamics of various composition of DGEBA/R45EPI mixtures having MDA as a curing agent were investigated. The phase separation behavior was quite dependent upon the composition variation. R45EPI itself can react with itself or with DGEBA without curing, therefore three-component system was considered in this mixture. For the numerical studies of this three- component mixture, a system that is composed of a reactive component-1 that is miscible with its growing molecules and another reactive component-2 that is not miscible with its growing molecules was considered with crosslinking reaction kinetics of the each component.

Modification of linear prepolymers to tailor heterogeneous network formation through photo-initiated Polymerization-Induced Phase Separation

PubMed Central

Szczepanski, Caroline R.; Stansbury, Jeffrey W.

2015-01-01

Polymerization-induced phase separation (PIPS) was studied in ambient photopolymerizations of triethylene glycol dimethacrylate (TEGDMA) modified by poly(methyl methacrylate) (PMMA). The molecular weight of PMMA and the rate of network formation (through incident UV-irradiation) were varied to influence both the promotion of phase separation through increases in overall free energy, as well as the extent to which phase development occurs during polymerization through diffusion prior to network gelation. The overall free energy of the polymerizing system increases with PMMA molecular weight, such that PIPS is promoted thermodynamically at low loading levels (5 wt%) of a higher molecular weight PMMA (120 kDa), while a higher loading level (20 wt%) is needed to induce PIPS with lower PMMA molecular weight (11 kDa), and phase separation was not promoted at any loading level tested of the lowest molecular weight PMMA (1 kDa). Due to these differences in overall free energy, systems modified by PMMA (11 kDa) underwent phase separation via Nucleation and Growth, and systems modified by PMMA (120 kDa), followed the Spinodal Decomposition mechanism. Despite differences in phase structure, all materials form a continuous phase rich in TEGDMA homopolymer. At high irradiation intensity (Io=20mW/cm2), the rate of network formation prohibited significant phase separation, even when thermodynamically preferred. A staged curing approach, which utilizes low intensity irradiation (Io=300µW/cm2) for the first ~50% of reaction to allow phase separation via diffusion, followed by a high intensity flood-cure to achieve a high degree of conversion, was employed to form phase-separated networks with reduced polymerization stress yet equivalent final conversion and modulus. PMID:26190865

Thermal vacancies and phase separation in bcc mixtures of helium-3 and helium-4

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

Fraass, Benedick Andrew

1980-01-01

Thermal vacancy concentrations in crystals of 3He- 4He mixtures have been determined. A new x-ray diffractometer-position sensitive detector system is used to make measurements of the absolute lattice parameter of the helium crystals with an accuracy of 300 ppM, and measurements of changes in lattice parameters to better than 60 ppM. The phase separation of the concentrated 3He- 4He mixtures has been studied in detail with the x-ray measurements. Vacancy concentrations in crystals with 99%, 51%, 28%, 12%, and 0% 3He have been determined. Phase separation has been studied in mixed crystals with concentrations of 51%, 28%, and 12% 3Hemore » and melting pressures between 3.0 and 6.1 MPa. The phase separation temperatures determined in this work are in general agreement with previous work. The pressure dependence of T c, the phase separation temperature for a 50% mixture, is found to be linear: dT c/dP = -34 mdeg/MPa. The x-ray measurements are used to make several comments on the low temperature phase diagram of the helium mixtures.« less

Understanding the mechanism of LCST phase separation of mixed ionic liquids in water by MD simulations.

PubMed

Zhao, Yuling; Wang, Huiyong; Pei, Yuanchao; Liu, Zhiping; Wang, Jianji

2016-08-17

Recently, it has been found experimentally that two different amino acid ionic liquids (ILs) can be mixed to show unique lowest critical solution temperature (LCST) phase separation in water. However, little is known about the mechanism of phase separation in these IL/water mixtures at the molecular level. In this work, five kinds of amino acid ILs were chosen to study the mechanism of LCST-type phase separation by molecular dynamics (MD) simulations. Toward this end, a series of all-atom MD simulations were carried out on the ternary mixtures consisting of two different ILs and water at different temperatures. The various interaction energies and radial distribution functions (RDFs) were calculated and analyzed for these mixed systems. It was found that for amino acid ILs, the -NH2 or -COOH group of one anion could have a hydrogen bonding interaction with the -COO(-) group of another anion. With the increase of temperature, this kind of hydrogen bonding interaction between anions was strengthened and then the anion-H2O electrostatic interaction was weakened, which led to the LCST-type phase separation of the mixed ILs in water. In addition, a series of MD simulations for [P6668]1[Lys]n[Asp]1-n/H2O systems were also performed to study the effect of the mixing ratio of ILs on phase separation. It was also noted that the experimental critical composition corresponding to the lowest critical solution temperature was well predicted from the total electrostatic interaction energies as a function of mole fraction of [P6668][Lys] in these systems. The conclusions drawn from this study may provide new insight into the LCST-type phase behavior of ILs in water, and motivate further studies on practical applications.

Enantiomeric separation of type I and type II pyrethroid insecticides with different chiral stationary phases by reversed-phase high-performance liquid chromatography.

PubMed

Zhang, Ping; Yu, Qian; He, Xiulong; Qian, Kun; Xiao, Wei; Xu, Zhifeng; Li, Tian; He, Lin

2018-04-01

The enantiomeric separation of type I (bifenthrin, BF) and type II (lambda-cyhalothrin, LCT) pyrethroid insecticides on Lux Cellulose-1, Lux Cellulose-3, and Chiralpak IC chiral columns was investigated by reversed-phase high-performance liquid chromatography. Methanol/water or acetonitrile/water was used as mobile phase at a flow rate of 0.8 mL/min. The effects of chiral stationary phase, mobile phase composition, column temperature, and thermodynamic parameters on enantiomer separation were carefully studied. Bifenthrin got a partial separation on Lux Cellulose-1 column and baseline separation on Lux Cellulose-3 column, while LCT enantiomers could be completely separated on both Lux Cellulose-1 and Lux Cellulose-3 columns. Chiralpak IC provided no separation ability for both BF and LCT. Retention factor (k) and selectivity factor (α) decreased with the column temperature increasing from 10°C to 40°C for both BF and LCT enantiomers. Thermodynamic parameters including ∆H and ∆S were also calculated, and the maximum R s were not always obtained at lowest temperature. Furthermore, the quantitative analysis methods for BF and LCT enantiomers in soil and water were also established. Such results provide a new approach for pyrethroid separation under reversed-phase condition and contribute to environmental risk assessment of pyrethroids at enantiomer level. © 2017 Wiley Periodicals, Inc.

The antagonistic role of chaotropic hexafluorophosphate anions and imidazolium cations composing ionic liquids applied as phase additives in the separation of tri-cyclic antidepressants.

PubMed

Caban, Magda; Stepnowski, Piotr

2017-05-15

The main advantage of alkylimidazolium cation-based ionic liquids (ILs) as phase additives in RP-HPLC is believed to be the suppression of deleterious residual free silanols in chemically modified silica stationary phases. However, up to now, the influence of ILs was usually evaluated having in mind a particular IL salt as one compound, not as a specific mixture of cations and anions. This in fact led to some misinterpretation of observed results, very often related to the suppression effect, while in fact caused by the nature of IL anions, which contribute to the elevated chaotropicity of the separation phases. In the present study, we have attempted to consider the effect gained due to the presence of both ionic liquid entities in the mobile phase used for the separation of basic compounds. Tri-cyclic antidepressants (TCAs) were taken as representative analytes. The effect of ILs on the chromatographic separation of TCAs was investigated in comparison to common mobile phase additives and by the presentation of retention factors, tailing factors and theoretical plates. In addition, an overloading study was performed for the IL-based phases for the first time. In general, it was found that the effect of chaotropic hexafluorophosphate anions in ILs is much stronger and opposite to that caused by imidazolium cations. The overloading study gives interesting information on how imidazolium cations affect the separation of cationic analytes. Finally, the usefulness of imidazolium-based ILs as mobile phase modifiers in the RP-HPLC separation of basic compounds was discussed. Copyright © 2017 Elsevier B.V. All rights reserved.

Hygroscopic and phase separation properties of ammonium sulfate/organics/water ternary solutions

NASA Astrophysics Data System (ADS)

Zawadowicz, M. A.; Proud, S. R.; Seppalainen, S. S.; Cziczo, D. J.

2015-08-01

Atmospheric aerosol particles are often partially or completely composed of inorganic salts, such as ammonium sulfate and sodium chloride, and therefore exhibit hygroscopic properties. Many inorganic salts have well-defined deliquescence and efflorescence points at which they take up and lose water, respectively. Field measurements have shown that atmospheric aerosols are not typically pure inorganic salt, instead, they often also contain organic species. There is ample evidence from laboratory studies that suggests that mixed particles exist in a phase-separated state, with an aqueous inorganic core and organic shell. Although phase separation has not been measured in situ, there is no reason it would not also take place in the atmosphere. Here, we investigate the deliquescence and efflorescence points, phase separation and ability to exchange gas-phase components of mixed organic and inorganic aerosol using a flow tube coupled with FTIR (Fourier transform infrared) spectroscopy. Ammonium sulfate aerosol mixed with organic polyols with different O : C ratios, including 1,4-butanediol, glycerol, 1,2,6-hexanetriol, 1,2-hexanediol, and 1,5-pentanediol have been investigated. Those constituents correspond to materials found in the atmosphere in great abundance and, therefore, particles prepared in this study should mimic atmospheric mixed-phase aerosol particles. Some results of this study tend to be in agreement with previous microscopy experiments, but others, such as phase separation properties of 1,2,6-hexanetriol, do not agree with previous work. Because the particles studied in this experiment are of a smaller size than those used in microscopy studies, the discrepancies found could be a size-related effect.

Comparing the selectivity and chiral separation of d- and l- fluorenylmethyloxycarbonyl chloride protected amino acids in analytical high performance liquid chromatography and supercritical fluid chromatography; evaluating throughput, economic and environmental impact.

PubMed

Vera, C M; Shock, D; Dennis, G R; Farrell, W; Shalliker, R A

2017-04-14

The chiral separation of d- and l- FMOC amino acids was undertaken using the Lux Cellulose-1 polysaccharide based chiral column in HPLC (normal phase and reverse phase) and SFC conditions. This was done to compare the relative selectivity and separation between the three separation modes and to evaluate the potential benefits of SFC separations with regards to resolution, throughput, economic and environmental impact. It was established that the separation of d- and l- FMOC amino acids in SFC displayed behaviours that were similar to both normal phase and reversed phase, rather than distinctly one or the other. Additionally, although reversed phase conditions yielded significantly higher resolution values between enantiomers across the range of amino acids studied, improvements in selectivity in SFC via the introduction of higher concentrations of formic acid in the mobile phase allowed for better resolution per unit of time. Moreover since the SFC mobile phase is composed mostly of recyclable CO 2 , there is a reduction in organic solvent consumption, which minimises the economic and environmental costs. Copyright © 2017. Published by Elsevier B.V.

Separation of piracetam derivatives on polysaccharide-based chiral stationary phases.

PubMed

Kažoka, H; Koliškina, O; Veinberg, G; Vorona, M

2013-03-15

High-performance liquid chromatography was used for the enantiomeric separation of two chiral piracetam derivatives. The suitability of six commercially available polysaccharide-based chiral stationary phases (CSPs) under normal phase mode for direct enantioseparation has been investigated. The influence of the CSPs as well the nature and content of an alcoholic modifier in the mobile phase on separation and elution order was studied. It was established that CSP Lux Amylose-2 shows high chiral recognition ability towards 4-phenylsubstituted piracetam derivatives. Copyright © 2013 Elsevier B.V. All rights reserved.

Dynamics of coarsening in multicomponent lipid vesicles with non-uniform mechanical properties

NASA Astrophysics Data System (ADS)

Funkhouser, Chloe M.; Solis, Francisco J.; Thornton, K.

2014-04-01

Multicomponent lipid vesicles are commonly used as a model system for the complex plasma membrane. One phenomenon that is studied using such model systems is phase separation. Vesicles composed of simple lipid mixtures can phase-separate into liquid-ordered and liquid-disordered phases, and since these phases can have different mechanical properties, this separation can lead to changes in the shape of the vesicle. In this work, we investigate the dynamics of phase separation in multicomponent lipid vesicles, using a model that couples composition to mechanical properties such as bending rigidity and spontaneous curvature. The model allows the vesicle surface to deform while conserving surface area and composition. For vesicles initialized as spheres, we study the effects of phase fraction and spontaneous curvature. We additionally initialize two systems with elongated, spheroidal shapes. Dynamic behavior is contrasted in systems where only one phase has a spontaneous curvature similar to the overall vesicle surface curvature and systems where the spontaneous curvatures of both phases are similar to the overall curvature. The bending energy contribution is typically found to slow the dynamics by stabilizing configurations with multiple domains. Such multiple-domain configurations are found more often in vesicles with spheroidal shapes than in nearly spherical vesicles.

Development of the Two Phase Flow Separator Experiment for a Reduced Gravity Aircraft Flight

NASA Technical Reports Server (NTRS)

Golliher, Eric; Gotti, Daniel; Owens, Jay; Gilkey, Kelly; Pham, Nang; Stehno, Philip

2016-01-01

The recent hardware development and testing of a reduced gravity aircraft flight experiment has provided valuable insights for the future design of the Two Phase Flow Separator Experiment (TPFSE). The TPFSE is scheduled to fly within the Fluids Integration Rack (FIR) aboard the International Space Station (ISS) in 2020. The TPFSE studies the operational limits of gas and liquid separation of passive cyclonic separators. A passive cyclonic separator utilizes only the inertia of the incoming flow to accomplish the liquid-gas separation. Efficient phase separation is critical for environmental control and life support systems, such as recovery of clean water from bioreactors, for long duration human spaceflight missions. The final low gravity aircraft flight took place in December 2015 aboard NASA's C9 airplane.

Green chiral HPLC enantiomeric separations using high temperature liquid chromatography and subcritical water on Chiralcel OD and Chiralpak AD.

PubMed

Droux, Serge; Félix, Guy

2011-01-01

We report here the application of subcritical water in chiral separations on two popular polysaccharide chiral stationary phases (CSPs): Chiralpak AD and Chiralcel OD. The behavior of these two CSPs was studied under reversed phase conditions at room temperature to discover the maximum percentage of water in the mobile phase, which provided the separation of enantiomers of flavanone and benzoin, respectively, in a reasonable time (i.e., less than 1 h). Then, the stability of Chiralpak AD and Chiralcel OD versus temperature was investigated and discussed. Chiralcel OD separation of flavanone racemate was obtained at 120 °C with water and 2-propanol (80/20) as the mobile phase, while benzoin racemate was separated in pure water at 160 °C. Separations of several racemates were also presented, and advantages and limitations of the technique were discussed. Copyright © 2011 Wiley Periodicals, Inc.

Optimization of the high-performance liquid chromatographic separation of a complex mixture containing urinary steroids, boldenone and bolasterone: application to urine samples.

PubMed

Gonzalo-Lumbreras, R; Izquierdo-Hornillos, R

2000-05-26

An HPLC separation of a complex mixture containing 13 urinary anabolics and corticoids, and boldenone and bolasterone (synthetic anabolics) has been carried out. The applied optimization method involved the use of binary, ternary and quaternary mobile phases containing acetonitrile, methanol or tetrahydrofuran as organic modifiers. The effect of different reversed-phase packings and temperature on the separation was studied. The optimum separation was achieved by using a water-acetonitrile (60:40, v/v) mobile phase in reversed-phase HPLC at 30 degrees C, allowing the separation of all the analytes in about 24 min. Calibration graphs were obtained using bolasterone or methyltestosterone as internal standards. Detection limits were in the range 0.012-0.107 microg ml(-1). The optimized separation was applied to the analysis, after liquid-liquid extraction, of human urine samples spiked with steroids.

Numerical study of gravity effects on phase separation in a swirl chamber.

PubMed

Hsiao, Chao-Tsung; Ma, Jingsen; Chahine, Georges L

2016-01-01

The effects of gravity on a phase separator are studied numerically using an Eulerian/Lagrangian two-phase flow approach. The separator utilizes high intensity swirl to separate bubbles from the liquid. The two-phase flow enters tangentially a cylindrical swirl chamber and rotate around the cylinder axis. On earth, as the bubbles are captured by the vortex formed inside the swirl chamber due to the centripetal force, they also experience the buoyancy force due to gravity. In a reduced or zero gravity environment buoyancy is reduced or inexistent and capture of the bubbles by the vortex is modified. The present numerical simulations enable study of the relative importance of the acceleration of gravity on the bubble capture by the swirl flow in the separator. In absence of gravity, the bubbles get stratified depending on their sizes, with the larger bubbles entering the core region earlier than the smaller ones. However, in presence of gravity, stratification is more complex as the two acceleration fields - due to gravity and to rotation - compete or combine during the bubble capture.

Creating Drug Solubilization Compartments via Phase Separation in Multicomponent Buccal Patches Prepared by Direct Hot Melt Extrusion-Injection Molding.

PubMed

Alhijjaj, Muqdad; Bouman, Jacob; Wellner, Nikolaus; Belton, Peter; Qi, Sheng

2015-12-07

Creating in situ phase separation in solid dispersion based formulations to allow enhanced functionality of the dosage form, such as improving dissolution of poorly soluble model drug as well as being mucoadhesive, can significantly maximize the in vitro and in vivo performance of the dosage form. This formulation strategy can benefit a wide range of solid dosage forms for oral and alternative routes of delivery. This study using buccal patches as an example created separated phases in situ of the buccal patches by selecting the excipients with different miscibility with each other and the model drug. The quaternary dispersion based buccal patches containing PEG, PEO, Tween 80, and felodipine were prepared by direct hot melt extrusion-injection molding (HME-IM). The partial miscibility between Tween 80 and semicrystalline PEG-PEO led to the phase separation after extrusion. The Tween phases acted as drug solubilization compartments, and the PEG-PEO phase had the primary function of providing mucoadhesion and carrier controlled dissolution. As felodipine was preferably solubilized in the amorphous regions of PEG-PEO, the high crystallinity of PEG-PEO resulted in an overall low drug solubilizing capacity. Tween 80 was added to improve the solubilization capacity of the system as the model drug showed good solubility in Tween. Increasing the drug loading led to the supersaturation of drug in Tween compartments and crystalline drug dispersed in PEG-PEO phases. The spatial distribution of these phase-separated compartments was mapped using X-ray micro-CT, which revealed that the domain size and heterogeneity of the phase separation increased with increasing the drug loading. The outcome of this study provides new insights into the applicability of in situ formed phase separation as a formulation strategy for the delivery of poorly soluble drugs and demonstrated the basic principle of excipient selection for such technology.

Exploring the dynamics of phase separation in colloid-polymer mixtures with long range attraction.

PubMed

Sabin, Juan; Bailey, Arthur E; Frisken, Barbara J

2016-06-28

We have studied the kinetics of phase separation and gel formation in a low-dispersity colloid - non-adsorbing polymer system with long range attraction using small-angle light scattering. This system exhibits two-phase and three-phase coexistence of gas, liquid and crystal phases when the strength of attraction is between 2 and 4kBT and gel phases when the strength of attraction is increased. For those samples that undergo macroscopic phase separation, whether to gas-crystal, gas-liquid or gas-liquid-crystal coexistence, we observe dynamic scaling of the structure factor and growth of a characteristic length scale that behaves as expected for phase separation in fluids. In samples that gel, the power law associated with the growth of the dominant length scale is not equal to 1/3, but appears to depend mainly on the strength of attraction, decreasing from 1/3 for samples near the coexistence region to 1/27 at 8kBT, over a wide range of colloid and polymer concentrations.

Experimental study of phase separation in dividing two phase flow

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

Qian Yong; Yang Zhilin; Xu Jijun

1996-12-31

Experimental study of phase separation of air-water two phase bubbly, slug flow in the horizontal T-junction is carried out. The influences of the inlet mass quality X1, mass extraction rate G3/G1, and fraction of extracted liquid QL3/QL1 on phase separation characteristics are analyzed. For the first time, the authors have found and defined pulsating run effect by the visual experiments, which show that under certain conditions, the down stream flow of the T-junction has strangely affected the phase redistribution of the junction, and firstly point out that the downstream geometric condition is very important to the study of phase separationmore » phenomenon of two-phase flow in a T-junction. This kind of phenomenon has many applications in the field of energy, power, petroleum and chemical industries, such as the loss of coolant accident (LOCA) caused by a small break in a horizontal coolant pipe in nuclear reactor, and the flip-flop effect in the natural gas transportation pipeline system, etc.« less

Relation between secondary doping and phase separation in PEDOT:PSS films

NASA Astrophysics Data System (ADS)

Donoval, Martin; Micjan, Michal; Novota, Miroslav; Nevrela, Juraj; Kovacova, Sona; Pavuk, Milan; Juhasz, Peter; Jagelka, Martin; Kovac, Jaroslav; Jakabovic, Jan; Cigan, Marek; Weis, Martin

2017-02-01

Conductive copolymer poly(3,4-ethylenedioxythiophene):poly(4-styrenesulfonate) (PEDOT:PSS) has been proposed as an alternative to transparent conductive oxides because of its flexibility, transparency, and low-cost production. Four different secondary dopants, namely N,N-dimethylformamide, ethyleneglycol, sorbitol, and dimethyl sulfoxide, have been used to improve the conductivity. The relation between the structure changes and conductivity enhancement is studied in detail. Atomic force microscopy study of the thin film surface reveals the phase separation of PEDOT and PSS. We demonstrate that secondary doping induces the phase separation as well as the conductivity enhancement.

Water-induced phase separation of miconazole-poly (vinylpyrrolidone-co-vinyl acetate) amorphous solid dispersions: Insights with confocal fluorescence microscopy.

PubMed

Saboo, Sugandha; Taylor, Lynne S

2017-08-30

The aim of this study was to evaluate the utility of confocal fluorescence microscopy (CFM) to study the water-induced phase separation of miconazole-poly (vinylpyrrolidone-co-vinyl acetate) (mico-PVPVA) amorphous solid dispersions (ASDs), induced during preparation, upon storage at high relative humidity (RH) and during dissolution. Different fluorescent dyes were added to drug-polymer films and the location of the dyes was evaluated using CFM. Orthogonal techniques, in particular atomic force microscopy (AFM) coupled with nanoscale infrared spectroscopy (AFM-nanoIR), were used to provide additional analysis of the drug-polymer blends. The initial miscibility of mico-PVPVA ASDs prepared under low humidity conditions was confirmed by AFM-nanoIR. CFM enabled rapid identification of drug-rich and polymer-rich phases in phase separated films prepared under high humidity conditions. The identity of drug- and polymer-rich domains was confirmed using AFM-nanoIR imaging and localized IR spectroscopy, together with Lorentz contact resonance (LCR) measurements. The CFM technique was then utilized successfully to further investigate phase separation in mico-PVPVA films exposed to high RH storage and to visualize phase separation dynamics following film immersion in buffer. CFM is thus a promising new approach to study the phase behavior of ASDs, utilizing drug and polymer specific dyes to visualize the evolution of heterogeneity in films exposed to water. Copyright © 2017 Elsevier B.V. All rights reserved.

Poly(1-allylimidazole)-grafted silica, a new specific stationary phase for reversed-phase and anion-exchange liquid chromatography.

PubMed

Sun, Min; Qiu, Hongdeng; Wang, Licheng; Liu, Xia; Jiang, Shengxiang

2009-05-01

A new specific stationary phase based on poly(1-allylimidazole)-grafted silica has been synthesized and characterized, by infrared spectra, elemental analysis, thermogravimetric analysis and X-ray photoelectron spectroscopy. The results of test showed that poly(1-allylimidazole) can effectively mask the residual silanol groups and reduce the adverse effect of residual silanol. Using this stationary phase, phenol compounds, aniline compounds, and polycyclic aromatic hydrocarbons were successfully separated with symmetric peak shapes in the reversed-phase chromatography. Inorganic anions (IO(3)(-), BrO(3)(-), Br(-), NO(3)(-), I(-), SCN(-)) were also separated completely in the anion-exchange chromatography using sodium chloride solution as the mobile phase. The effects of pH and the concentration of eluent on the separation of inorganic anions were studied. The separation mechanism appears to involve the mixed interactions of hydrogen bonding, hydrophobic, pi-pi, electrostatic, and anion-exchange interactions.

Preparation and evaluation of a silica-based 1-alkyl-3-(propyl-3-sulfonate) imidazolium zwitterionic stationary phase for high-performance liquid chromatography.

PubMed

Qiu, Hongdeng; Jiang, Qiong; Wei, Zheng; Wang, Xusheng; Liu, Xia; Jiang, Shengxiang

2007-09-07

A new zwitterionic stationary phase based on silica bonded with 1-alkyl-3-(propyl-3-sulfonate) imidazolium was synthesized and characterized in this paper. The materials have been confirmed and evaluated by elemental analysis, thermogravimetric analysis and X-ray photoelectron spectroscopy. Potassium and calcium were separated simultaneously with several common inorganic anions including an iodate, chloride, bromide, nitrate and iodide on the phase. The effects of the concentration, organic solvent and pH of the eluent on the separation of anions were studied. Operated in the anion-exchange mode, this new stationary phase shows considerable promise for the separation of anions. Bases, vitamins and three imidazolium ionic liquids with different alkyl chains are also separated successfully on this column. The stationary phase has multiple retention mechanisms, such as anion-exchange, electrostatic attraction and repulsion interactions, and hydrophobic interaction between the zwitterionic stationary phase and specimens.

Investigations on transparent liquid-miscibility gap systems

NASA Technical Reports Server (NTRS)

Lacy, L. L.; Nishioka, G.; Ross, S.

1979-01-01

Sedimentation and phase separation is a well known occurrence in monotectic or miscibility gap alloys. Previous investigations indicate that it may be possible to prepare such alloys in a low-gravity space environment but recent experiments indicate that there may be nongravity dependent phase separation processes which can hinder the formation of such alloys. Such phase separation processes are studied using transparent liquid systems and holography. By reconstructing holograms into a commercial-particle-analysis system, real time computer analysis can be performed on emulsions with diameters in the range of 5 micrometers or greater. Thus dynamic effects associated with particle migration and coalescence can be studied. Characterization studies on two selected immiscible systems including an accurate determination of phase diagrams, surface and interfacial tension measurements, surface excess and wetting behavior near critical solution temperatures completed.

Supramolecular separation mechanism of pentafluorophenyl column using ibuprofen and omeprazole as markers: LC-MS and simulation study.

PubMed

Hussain, Afzal; AlAjmi, Mohamed F; Ali, Imran

2018-06-01

The pentafluorophenyl (PFP) column is emerging as a new advancement in separation science to analyze a wide range of analytes and, thus, its separation mechanism at supramolecular level is significant. We developed a mechanism for the separation of ibuprofen and omeprazole using different combinations (ranging from 50:50 to 60:40) of water-acetonitrile containing 0.1% formic acid as the mobile phase. The column used was Waters Acquity UPLC HSS PFP (75 × 2.1 mm, 1.8 μm). The reverse order of elution was observed in different combinations of the mobile phases. The docking study indicated hydrogen bonding between ibuprofen and PFP stationary phase (binding energy was -11.30 kJ/mol). Separation at PFP stationary phase is controlled by hydrogen bonding along with π-π interactions. This stationary phase may be used to analyze both aromatic and aliphatic analytes. The developed mechanism will be useful to separate various analytes by considering the possible interactions, leading to saving of energy, time and money. In addition, this work will be highly useful in preparative chromatography where separation is the major problem at a large scale. Moreover, the developed LC-MS-QTOF method may be used to analyze ibuprofen and omeprazole in an unknown sample owing to the low value of detection limits. Copyright © 2018 John Wiley & Sons, Ltd.

Preparative separation of the polar part from the rhizomes of Anemarrhena asphodeloides using a hydrophilic C18 stationary phase.

PubMed

Cai, Jianfeng; Xin, Huaxia; Cheng, Lingping; Fu, YanHui; Jiang, Dasen; Feng, Jiatao; Fu, Qing; Jin, Yu; Liang, Xinmiao

2017-09-15

The goal of this study was to develop a method that utilized a hydrophilic C18 stationary phase in the preparative high performance liquid chromatography to isolate the polar part from the rhizomes of Anemarrhena asphodeloides. The results showed that an initial mobile phase of pure water for the separation could greatly increase the retention and solubility of the polar compounds at the preparative scale. Introducing polar groups on the surface of the hydrophilic C18 column together with the use of optimized mobile phase compositions improved the column separation selectivity for polar compounds. Eleven previously undescribed compounds in Anemarrhena asphodeloides were obtained, indicating that the method developed in this study would facilitate the purification and separation of the polar part of traditional Chinese medicines. Copyright © 2017 Elsevier B.V. All rights reserved.

Separation of Iron Phase and P-Bearing Slag Phase from Gaseous-Reduced, High-Phosphorous Oolitic Iron Ore at 1473 K (1200 °C) by Super Gravity

NASA Astrophysics Data System (ADS)

Gao, Jintao; Zhong, Yiwei; Guo, Lei; Guo, Zhancheng

2016-04-01

In situ observation on the morphology evolution and phosphorous migration of gaseous-reduced, high-phosphorous oolitic iron ore during the melting process was carried out with a high-temperature confocal scanning laser microscope. The results showed that 1473 K (1200 °C) was a critical temperature at which the gangue minerals started to form into the slag phase while the iron grains remained in a solid state; in addition, the phosphorus remained in the slag phase. Since the separation of iron grains and P-bearing slag was not achieved at the low temperature under the conventional conditions, separate experiments of the iron phase and the P-bearing slag phase from gaseous-reduced, high-phosphorous oolitic iron ore at 1473 K (1200 °C) by super gravity were carried out in this study. Based on the iron-slag separation by super gravity, phosphorus was removed effectively from the iron phase at the temperature below the melting point of iron. Iron grains moved along the super-gravity direction, joined, and concentrated as the iron phase on the filter, whereas the slag phase containing apatite crystals broke through the barriers of the iron grains and went through the filter. Consequently, increasing the gravity coefficient was definitely beneficial for the separation of the P-bearing slag phase from the iron phase. With the gravity coefficient of G = 1200, the mass fractions of separated slag and iron phases were close to their respective theoretical values, and the mass fraction of MFe in the separated iron phase was up to 98.09 wt pct and that of P was decreased to 0.083 wt pct. The recovery of MFe in the iron phase and that of P in the slag phase were up to 99.19 and 95.83 pct, respectively.

Distinction of synthetic dl-α-tocopherol from natural vitamin E (d-α-tocopherol) by reversed-phase liquid chromatography. Enhanced selectivity of a polymeric C18 stationary phase at low temperature and/or at high pressure.

PubMed

Yui, Yuko; Miyazaki, Shota; Ma, Yan; Ohira, Masayoshi; Fiehn, Oliver; Ikegami, Tohru; McCalley, David V; Tanaka, Nobuo

2016-06-10

Separation of diastereomers of dl-α-tocopherol was studied by reversed-phase liquid chromatography using three types of stationary phases, polymeric ODS, polymeric C30, and monomeric ODS. Polymeric ODS stationary phase (Inertsil ODS-P, 3mmID, 20cm) was effective for the separation of the isomers created by the presence of three chiral centers on the alkyl chain of synthetic dl-α-tocopherol. Considerable improvement of the separation of isomers was observed on ODS-P phase at high pressure and at low temperature. Complete separation of four pairs of diastereomers was achieved at 12.0°C, 536bar, while three peaks were observed when the separation was carried out either at 12.0°C at low pressure or at 20°C at 488bar. Higher temperature (30.0°C) with the ODS-P phase resulted in only partial separation of the diastereomers even at high pressure. Only slight resolution was observed for the mixture of diastereomers with the C30 stationary phase (Inertsil C30) at 12.0°C and 441bar, although the stationary phase afforded greater resolution for β- and γ-tocopherol than ODS-P. A monomeric C18 stationary phase did not show any separation at 12.0°C and 463bar. The results suggest that the binding site of the polymeric ODS-P phase is selective for flexible alkyl chains that provided the longest retention for the natural form, (R,R,R) form, and the enantiomer, (S,S,S) form, of dl-α-tocopherol. Copyright © 2016. Published by Elsevier B.V.

Laser-induced phase separation of silicon carbide

PubMed Central

Choi, Insung; Jeong, Hu Young; Shin, Hyeyoung; Kang, Gyeongwon; Byun, Myunghwan; Kim, Hyungjun; Chitu, Adrian M.; Im, James S.; Ruoff, Rodney S.; Choi, Sung-Yool; Lee, Keon Jae

2016-01-01

Understanding the phase separation mechanism of solid-state binary compounds induced by laser–material interaction is a challenge because of the complexity of the compound materials and short processing times. Here we present xenon chloride excimer laser-induced melt-mediated phase separation and surface reconstruction of single-crystal silicon carbide and study this process by high-resolution transmission electron microscopy and a time-resolved reflectance method. A single-pulse laser irradiation triggers melting of the silicon carbide surface, resulting in a phase separation into a disordered carbon layer with partially graphitic domains (∼2.5 nm) and polycrystalline silicon (∼5 nm). Additional pulse irradiations cause sublimation of only the separated silicon element and subsequent transformation of the disordered carbon layer into multilayer graphene. The results demonstrate viability of synthesizing ultra-thin nanomaterials by the decomposition of a binary system. PMID:27901015

Bioinspired Non-iridescent Structural Color from Polymer Blend Thin Films

NASA Astrophysics Data System (ADS)

Nallapaneni, Asritha; Shawkey, Matthew; Karim, Alamgir

Colors exhibited in biological species are either due to natural pigments, sub-micron structural variation or both. Structural colors thus exhibited can be iridescent (ID) or non-iridescent (NID) in nature. NID colors originate due to interference and coherent scattering of light with quasi-ordered micro- and nano- structures. Specifically, in Eastern Bluebird (Sialia sialis) these nanostructures develop as a result of phase separation of β-keratin from cytoplasm present in cells. We replicate these structures via spinodal blend phase separation of PS-PMMA thin films. Colors of films vary from ultraviolet to blue. Scattering of UV-visible light from selectively leeched phase separated blends are studied in terms of varying domain spacing (200nm to 2 μm) of film. We control these parameters by tuning annealing time and temperature. Angle-resolved spectroscopy studies suggest that the films are weakly iridescent and scattering from phase-separated films is more diffused when compared to well-mixed films. This study offers solutions to several color-based application in paints and coatings industry.

Capillary electrochromatography and capillary electrochromatography-electrospray mass spectrometry for the separation of non-steroidal anti-inflammatory drugs.

PubMed

Desiderio, C; Fanali, S

2000-10-20

In this study capillary electrochromatography (CEC) was utilized for the separation of ten non-steroidal anti-inflammatory drugs (NSAIDs). Experiments were carried out in a commercially available CE instrument using a packed capillary with RP-18 silica particles where the stationary phase completely filled the capillary. The mobile phase consisted of a mixture of ammonium formate buffer pH 2.5 and acetonitrile. Selectivity and resolution were studied changing the pH and the concentration of the buffer, the acetonitrile content mobile phase and the capillary temperature. The optimum experimental conditions for CEC separation of the studied drug mixture were found using 50 mM ammonium formate pH 2.5-acetonitrile (40:60) at 25 degrees C. The CEC capillary was coupled to an electrospray mass spectrometer for the characterization of the NSAIDs. A mobile phase composed by the same buffer but with a higher concentration of acetonitrile (90%) was used in order to speed up the separation of analytes.

Extent and mechanism of phase separation during the extrusion of calcium phosphate pastes.

PubMed

O'Neill, Rory; McCarthy, Helen O; Cunningham, Eoin; Montufar, Edgar; Ginebra, Maria-Pau; Wilson, D Ian; Lennon, Alex; Dunne, Nicholas

2016-02-01

The aim of this study was to increase understanding of the mechanism and dominant drivers influencing phase separation during ram extrusion of calcium phosphate (CaP) paste for orthopaedic applications. The liquid content of extrudate was determined, and the flow of liquid and powder phases within the syringe barrel during extrusion were observed, subject to various extrusion parameters. Increasing the initial liquid-to-powder mass ratio, LPR, (0.4-0.45), plunger rate (5-20 mm/min), and tapering the barrel exit (45°-90°) significantly reduced the extent of phase separation. Phase separation values ranged from (6.22 ± 0.69 to 18.94 ± 0.69 %). However altering needle geometry had no significant effect on phase separation. From powder tracing and liquid content determination, static zones of powder and a non-uniform liquid distribution was observed within the barrel. Measurements of extrudate and paste LPR within the barrel indicated that extrudate LPR remained constant during extrusion, while LPR of paste within the barrel decreased steadily. These observations indicate the mechanism of phase separation was located within the syringe barrel. Therefore phase separation can be attributed to either; (1) the liquid being forced downstream by an increase in pore pressure as a result of powder consolidation due to the pressure exerted by the plunger or (2) the liquid being drawn from paste within the barrel, due to suction, driven by dilation of the solids matrix at the barrel exit. Differentiating between these two mechanisms is difficult; however results obtained suggest that suction is the dominant phase separation mechanism occurring during extrusion of CaP paste.

Formation of ion clusters in the phase separated structures of neutral-charged polymer blends

NASA Astrophysics Data System (ADS)

Kwon, Ha-Kyung; Olvera de La Cruz, Monica

2015-03-01

Polyelectrolyte blends, consisting of at least one charged species, are promising candidate materials for fuel cell membranes, for their mechanical stability and high selectivity for proton conduction. The phase behavior of the blends is important to understand, as this can significantly affect the performance of the device. The phase behavior is controlled by χN, the Flory-Huggins parameter multiplied by the number of mers, as well as the electrostatic interactions between the charged backbone and the counterions. It has recently been shown that local ionic correlations, incorporated via liquid state (LS) theory, enhance phase separation of the blend, even in the absence of polymer interactions. In this study, we show phase diagrams of neutral-charged polymer blends including ionic correlations via LS theory. In addition to enhanced phase separation at low χN, the blends show liquid-liquid phase separation at high electrostatic interaction strengths. Above the critical strength, the charged polymer phase separates into ion-rich and ion-poor regions, resulting in the formation of ion clusters within the charged polymer phase. This can be shown by the appearance of multiple spinodal and critical points, indicating the coexistence of several charge separated phases. This work was performed under the following financial assistance award 70NANB14H012 from U.S. Department of Commerce, National Institute of Standards and Technology as part of the Center for Hierarchical Materials Design (CHiMaD).

Thermodynamics and structural transition of binary atomic Bose-Fermi mixtures in box or harmonic potentials: A path-integral study

NASA Astrophysics Data System (ADS)

Kim, Tom; Chien, Chih-Chun

2018-03-01

Experimental realizations of a variety of atomic binary Bose-Fermi mixtures have brought opportunities for studying composite quantum systems with different spin statistics. The binary atomic mixtures can exhibit a structural transition from a mixture into phase separation as the boson-fermion interaction increases. By using a path-integral formalism to evaluate the grand partition function and the thermodynamic grand potential, we obtain the effective potential of binary Bose-Fermi mixtures. Thermodynamic quantities in a broad range of temperatures and interactions are also derived. The structural transition can be identified as a loop of the effective potential curve, and the volume fraction of phase separation can be determined by the lever rule. For 6Li-7Li and 6Li-41K mixtures, we present the phase diagrams of the mixtures in a box potential at zero and finite temperatures. Due to the flexible densities of atomic gases, the construction of phase separation is more complicated when compared to conventional liquid or solid mixtures where the individual densities are fixed. For harmonically trapped mixtures, we use the local density approximation to map out the finite-temperature density profiles and present typical trap structures, including the mixture, partially separated phases, and fully separated phases.

Effect of Coriolis force on counter-current chromatographic separation by centrifugal partition chromatography.

PubMed

Ikehata, Jun-Ichi; Shinomiya, Kazufusa; Kobayashi, Koji; Ohshima, Hisashi; Kitanaka, Susumu; Ito, Yoichiro

2004-02-06

The effect of Coriolis force on the counter-current chromatographic separation was studied using centrifugal partition chromatography (CPC) with four different two-phase solvent systems including n-hexane-acetonitrile (ACN); tert-butyl methyl ether (MtBE)-aqueous 0.1% trifluoroacetic acid (TFA) (1:1); MtBE-ACN-aqueous 0.1% TFA (2:2:3); and 12.5% (w/w) polyethylene glycol (PEG) 1000-12.5% (w/w) dibasic potassium phosphate. Each separation was performed by eluting either the upper phase in the ascending mode or the lower phase in the descending mode, each in clockwise (CW) and counterclockwise column rotation. Better partition efficiencies were attained by the CW rotation in both mobile phases in all the two-phase solvent systems examined. The mathematical analysis also revealed the Coriolis force works favorably under the CW column rotation for both mobile phases. The overall results demonstrated that the Coriolis force produces substantial effects on CPC separation in both organic-aqueous and aqueous-aqueous two-phase systems.

Limitation of predictive 2-D liquid chromatography in reducing the database search space in shotgun proteomics: in silico studies.

PubMed

Moskovets, Eugene; Goloborodko, Anton A; Gorshkov, Alexander V; Gorshkov, Mikhail V

2012-07-01

A two-dimensional (2-D) liquid chromatography (LC) separation of complex peptide mixtures that combines a normal phase utilizing hydrophilic interactions and a reversed phase offers reportedly the highest level of 2-D LC orthogonality by providing an even spread of peptides across multiple LC fractions. Matching experimental peptide retention times to those predicted by empirical models describing chromatographic separation in each LC dimension leads to a significant reduction in a database search space. In this work, we calculated the retention times of tryptic peptides separated in the C18 reversed phase at different separation conditions (pH 2 and pH 10) and in TSK gel Amide-80 normal phase. We show that retention times calculated for different 2-D LC separation schemes utilizing these phases start to correlate once the mass range of peptides under analysis becomes progressively narrow. This effect is explained by high degree of correlation between retention coefficients in the considered phases. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Lo/Ld phase coexistence modulation induced by GM1.

PubMed

Puff, Nicolas; Watanabe, Chiho; Seigneuret, Michel; Angelova, Miglena I; Staneva, Galya

2014-08-01

Lipid rafts are assumed to undergo biologically important size-modulations from nanorafts to microrafts. Due to the complexity of cellular membranes, model systems become important tools, especially for the investigation of the factors affecting "raft-like" Lo domain size and the search for Lo nanodomains as precursors in Lo microdomain formation. Because lipid compositional change is the primary mechanism by which a cell can alter membrane phase behavior, we studied the effect of the ganglioside GM1 concentration on the Lo/Ld lateral phase separation in PC/SM/Chol/GM1 bilayers. GM1 above 1mol % abolishes the formation of the micrometer-scale Lo domains observed in GUVs. However, the apparently homogeneous phase observed in optical microscopy corresponds in fact, within a certain temperature range, to a Lo/Ld lateral phase separation taking place below the optical resolution. This nanoscale phase separation is revealed by fluorescence spectroscopy, including C12NBD-PC self-quenching and Laurdan GP measurements, and is supported by Gaussian spectral decomposition analysis. The temperature of formation of nanoscale Lo phase domains over an Ld phase is determined, and is shifted to higher values when the GM1 content increases. A "morphological" phase diagram could be made, and it displays three regions corresponding respectively to Lo/Ld micrometric phase separation, Lo/Ld nanometric phase separation, and a homogeneous Ld phase. We therefore show that a lipid only-based mechanism is able to control the existence and the sizes of phase-separated membrane domains. GM1 could act on the line tension, "arresting" domain growth and thereby stabilizing Lo nanodomains. Copyright © 2014 Elsevier B.V. All rights reserved.

Experimental Investigation and Thermodynamic Assessment of Phase Equilibria in the PLLA/Dioxane/Water Ternary System for Applications in the Biomedical Field.

PubMed

Ruggiero, Flavia; Netti, Paolo Antonio; Torino, Enza

2015-12-01

Fundamental understanding of thermodynamic of phase separation plays a key role in tuning the desired features of biomedical devices. In particular, phase separation of ternary solution is of remarkable interest in processes to obtain biodegradable and biocompatible architectures applied as artificial devices to repair, replace, or support damaged tissues or organs. In these perspectives, thermally induced phase separation (TIPS) is the most widely used technique to obtained porous morphologies and, in addition, among different ternary systems, polylactic acid (PLLA)/dioxane/water has given promising results and has been largely studied. However, to increase the control of TIPS-based processes and architectures, an investigation of the basic energetic phenomena occurring during phase separation is still required. Here we propose an experimental investigation of the selected ternary system by using isothermal titration calorimetric approach at different solvent/antisolvent ratio and a thermodynamic explanation related to the polymer-solvents interactions in terms of energetic contribution to the phase separation process. Furthermore, relevant information about the phase diagrams and interaction parameters of the studied systems are furnished in terms of liquid-liquid miscibility gap. Indeed, polymer-solvents interactions are responsible for the mechanism of the phase separation process and, therefore, of the final features of the morphologies; the knowledge of such data is fundamental to control processes for the production of membranes, scaffolds and several nanostructures. The behavior of the polymer at different solvent/nonsolvent ratios is discussed in terms of solvation mechanism and a preliminary contribution to the understanding of the role of the hydrogen bonding in the interface phenomena is also reported. It is the first time that thermodynamic data of a ternary system are collected by mean of nano-isothermal titration calorimetry (nano-ITC). Supporting Information is available.

Effect of the Hartmann number on phase separation controlled by magnetic field for binary mixture system with large component ratio

NASA Astrophysics Data System (ADS)

Heping, Wang; Xiaoguang, Li; Duyang, Zang; Rui, Hu; Xingguo, Geng

2017-11-01

This paper presents an exploration for phase separation in a magnetic field using a coupled lattice Boltzmann method (LBM) with magnetohydrodynamics (MHD). The left vertical wall was kept at a constant magnetic field. Simulations were conducted by the strong magnetic field to enhance phase separation and increase the size of separated phases. The focus was on the effect of magnetic intensity by defining the Hartmann number (Ha) on the phase separation properties. The numerical investigation was carried out for different governing parameters, namely Ha and the component ratio of the mixed liquid. The effective morphological evolutions of phase separation in different magnetic fields were demonstrated. The patterns showed that the slant elliptical phases were created by increasing Ha, due to the formation and increase of magnetic torque and force. The dataset was rearranged for growth kinetics of magnetic phase separation in a plot by spherically averaged structure factor and the ratio of separated phases and total system. The results indicate that the increase in Ha can increase the average size of separated phases and accelerate the spinodal decomposition and domain growth stages. Specially for the larger component ratio of mixed phases, the separation degree was also significantly improved by increasing magnetic intensity. These numerical results provide guidance for setting the optimum condition for the phase separation induced by magnetic field.

Comparison of analytical protein separation characteristics for three amine-based capillary-channeled polymer (C-CP) stationary phases.

PubMed

Jiang, Liuwei; Marcus, R Kenneth

2016-02-01

Capillary-channeled polymer (C-CP) fiber stationary phases are finding utility in the realms of protein analytics as well as downstream processing. We have recently described the modification of poly(ethylene terephthalate) (PET) C-CP fibers to affect amine-rich phases for the weak anion-exchange (WAX) separation of proteins. Polyethylenimine (PEI) is covalently coupled to the PET surface, with subsequent cross-linking imparted by treatment with 1,4-butanediol diglycidyl ether (BUDGE). These modifications yield vastly improved dynamic binding capacities over the unmodified fibers. We have also previously employed native (unmodified) nylon 6 C-CP fibers as weak anion/cation-exchange (mixed-mode) and hydrophobic interaction chromatography (HIC) phases for protein separations. Polyamide, nylon 6, consists of amide groups along the polymer backbone, with primary amines and carboxylic acid end groups. The analytical separation characteristics of these three amine-based C-CP fiber phases are compared here. Each of the C-CP fiber columns in this study was shown to be able to separate a bovine serum albumin/hemoglobin/lysozyme mixture at high mobile phase linear velocity (∼70 mm s(-1)) but with different elution characteristics. These differences reflect the types of protein-surface interactions that are occurring, based on the active group composition of the fiber surfaces. This study provides important fundamental understanding for the development of surface-modified C-CP fiber columns for protein separation.

A Physical Model for Three-Phase Compaction in Silicic Magma Reservoirs

NASA Astrophysics Data System (ADS)

Huber, Christian; Parmigiani, Andrea

2018-04-01

We develop a model for phase separation in magma reservoirs containing a mixture of silicate melt, crystals, and fluids (exsolved volatiles). The interplay between the three phases controls the dynamics of phase separation and consequently the chemical and physical evolution of magma reservoirs. The model we propose is based on the two-phase damage theory approach of Bercovici et al. (2001, https://doi.org/10.1029/2000JB900430) and Bercovici and Ricard (2003, https://doi.org/10.1046/j.1365-246X.2003.01854.x) because it offers the leverage of considering interface (in the macroscopic limit) between phases that can deform depending on the mechanical work and phase changes taking place locally in the magma. Damage models also offer the advantage that pressure is defined uniquely to each phase and does not need to be equal among phases, which will enable us to consider, in future studies, the large capillary pressure at which fluids are mobilized in mature, crystal-rich, magma bodies. In this first analysis of three-phase compaction, we solve the three-phase compaction equations numerically for a simple 1-D problem where we focus on the effect of fluids on the efficiency of melt-crystal separation considering the competition between viscous and buoyancy stresses only. We contrast three sets of simulations to explore the behavior of three-phase compaction, a melt-crystal reference compaction scenario (two-phase compaction), a three-phase scenario without phase changes, and finally a three-phase scenario with a parameterized second boiling (crystallization-induced exsolution). The simulations show a dramatic difference between two-phase (melt crystals) and three-phase (melt-crystals-exsolved volatiles) compaction-driven phase separation. We find that the presence of a lighter, significantly less viscous fluid hinders melt-crystal separation.

A two-dimensional phase separation on the spherical surface of the metallic glass Au55Pb22.5Sb22.5

NASA Technical Reports Server (NTRS)

Lee, M. C.; Johnson, W. L.

1982-01-01

Recent experiments indicate that a phase separation in a spherical sample of the metallic glass Au55Pb22.5Sb22.5 occurs near the surface of the sphere. This strongly suggests either a contribution of surface-free energy to the decomposition process or a possible influence of near surface impurities absorbed during synthesis of the sphere. The surface phase separation has been studied as a function of cooling rate of the sphere. At high cooling rates (small sphere sizes), the surface separation disappears altogether suggesting that the surface of the parent liquid droplet is initially homogeneous.

3D CFD simulation of Multi-phase flow separators

NASA Astrophysics Data System (ADS)

Zhu, Zhiying

2017-10-01

During the exploitation of natural gas, some water and sands are contained. It will be better to separate water and sands from natural gas to insure favourable transportation and storage. In this study, we use CFD to analyse the effect of multi-phase flow separator, whose detailed geometrical parameters are designed in advanced. VOF model and DPM are used here. From the results of CFD, we can draw a conclusion that separated effect of multi-phase flow achieves better results. No solid and water is carried out from gas outlet. CFD simulation provides an economical and efficient approach to shed more light on details of the flow behaviour.

Influence of particle size and shell thickness of core-shell packing materials on optimum experimental conditions in preparative chromatography.

PubMed

Horváth, Krisztián; Felinger, Attila

2015-08-14

The applicability of core-shell phases in preparative separations was studied by a modeling approach. The preparative separations were optimized for two compounds having bi-Langmuir isotherms. The differential mass balance equation of chromatography was solved by the Rouchon algorithm. The results show that as the size of the core increases, larger particles can be used in separations, resulting in higher applicable flow rates, shorter cycle times. Due to the decreasing volume of porous layer, the loadability of the column dropped significantly. As a result, the productivity and economy of the separation decreases. It is shown that if it is possible to optimize the size of stationary phase particles for the given separation task, the use of core-shell phases are not beneficial. The use of core-shell phases proved to be advantageous when the goal is to build preparative column for general purposes (e.g. for purification of different products) in small scale separations. Copyright © 2015 Elsevier B.V. All rights reserved.

Hygroscopic and phase separation properties of ammonium sulfate/organic/water ternary solutions

NASA Astrophysics Data System (ADS)

Zawadowicz, M. A.; Proud, S. R.; Seppalainen, S. S.; Cziczo, D. J.

2015-03-01

Atmospheric aerosol particles are often partially or completely composed of inorganic salts, such as ammonium sulfate and sodium chloride, and therefore exhibit hygroscopic properties. Many inorganic salts have well-defined deliquescence and efflorescence points at which they take up and lose water, respectively. Deliquescence and efflorescence of simple inorganic salt particles have been investigated by a variety of methods, such as IR spectroscopy, tandem mobility analysis and electrodynamic balance. Field measurements have shown that atmospheric aerosols are not typically pure inorganic salt, instead they often also contain organic species. There is ample evidence from laboratory studies that suggests that mixed particles exist in a phase-separated state, with an aqueous inorganic core and organic shell. Although phase separation has not been measured in situ, there is no reason it would not also take place in the atmosphere. Many recent studies have focused on microscopy techniques that require deposition of the aerosol on a glass slide, possibly changing its surface properties. Here, we investigate the deliquescence and efflorescence points, phase separation and ability to exchange gas-phase components of mixed organic and inorganic aerosol using a flow tube coupled with FTIR spectroscopy. Ammonium sulfate aerosol mixed with organic polyols with different O : C ratios, including 1,4-butanediol, glycerol, 1,2,6-hexanetriol, 1,2-hexanediol, and 1,5-pentanediol have been investigated. Those constituents correspond to materials found in the atmosphere in great abundance, and therefore, particles prepared in this study should mimic atmospheric mixed phase aerosol particles. The results of this study tend to be in agreement with previous microscopy experiments, with several key differences, which possibly reveal a size-dependent effect on phase separation in organic/inorganic aerosol particles.

Liquid chromatographic separation and thermodynamic investigation of lorcaserin hydrochloride enantiomers on immobilized amylose-based chiral stationary phase.

PubMed

Wani, Dattatraya V; Rane, Vipul P; Mokale, Santosh N

2018-03-01

A novel liquid chromatographic method was developed for enantiomeric separation of lorcaserin hydrochloride on Chiralpak IA column containing chiral stationary phase immobilized with amylose tris (3.5-dimethylphenylcarbamate) as chiral selector. Baseline separation with resolution greater than 4 was achieved using mobile phase containing mixture of n-hexane/ethanol/methanol/diethylamine (95:2.5:2.5:0.1, v/v/v/v) at a flow rate of 1.2 mL/min. The limit of detection and limit of quantification of the S-enantiomer were found to be 0.45 and 1.5 μg/mL, respectively; the developed method was validated as per ICH guideline. The influence of column oven temperatures studied in the range of 20°C to 50°C on separation was studied; from this, retention, separation, and resolution were investigated. The thermodynamic parameters ΔH°, ΔS°, and ΔG° were evaluated from van't Hoff plots,(Ink' versus 1/T) and used to explain the strength of interaction between enantiomers and immobilized amylose-based chiral stationary phase. © 2017 Wiley Periodicals, Inc.

Identifying Effective Design Approaches to Allocate Genotypes in Two-Phase Designs: A Case Study in Pelargonium zonale.

PubMed

Molenaar, Heike; Boehm, Robert; Piepho, Hans-Peter

2017-01-01

Robust phenotypic data allow adequate statistical analysis and are crucial for any breeding purpose. Such data is obtained from experiments laid out to best control local variation. Additionally, experiments frequently involve two phases, each contributing environmental sources of variation. For example, in a former experiment we conducted to evaluate production related traits in Pelargonium zonale , there were two consecutive phases, each performed in a different greenhouse. Phase one involved the propagation of the breeding strains to obtain the stem cutting count, and phase two involved the assessment of root formation. The evaluation of the former study raised questions regarding options for improving the experimental layout: (i) Is there a disadvantage to using exactly the same design in both phases? (ii) Instead of generating a separate layout for each phase, can the design be optimized across both phases, such that the mean variance of a pair-wise treatment difference (MVD) can be decreased? To answer these questions, alternative approaches were explored to generate two-phase designs either in phase-wise order (Option 1) or across phases (Option 2). In Option 1 we considered the scenarios (i) using in both phases the same experimental design and (ii) randomizing each phase separately. In Option 2, we considered the scenarios (iii) generating a single design with eight replicates and splitting these among the two phases, (iv) separating the block structure across phases by dummy coding, and (v) design generation with optimal alignment of block units in the two phases. In both options, we considered the same or different block structures in each phase. The designs were evaluated by the MVD obtained by the intra-block analysis and the joint inter-block-intra-block analysis. The smallest MVD was most frequently obtained for designs generated across phases rather than for each phase separately, in particular when both phases of the design were separated with a single pseudo-level. The joint optimization ensured that treatment concurrences were equally balanced across pairs, one of the prerequisites for an efficient design. The proposed alternative approaches can be implemented with any model-based design packages with facilities to formulate linear models for treatment and block structures.

A novel mechanical model for phase-separation in debris flows

NASA Astrophysics Data System (ADS)

Pudasaini, Shiva P.

2015-04-01

Understanding the physics of phase-separation between solid and fluid phases as a two-phase mass moves down slope is a long-standing challenge. Here, I propose a fundamentally new mechanism, called 'separation-flux', that leads to strong phase-separation in avalanche and debris flows. This new model extends the general two-phase debris flow model (Pudasaini, 2012) to include a separation-flux mechanism. The new flux separation mechanism is capable of describing and controlling the dynamically evolving phase-separation, segregation, and/or levee formation in a real two-phase, geometrically three-dimensional debris flow motion and deposition. These are often observed phenomena in natural debris flows and industrial processes that involve the transportation of particulate solid-fluid mixture material. The novel separation-flux model includes several dominant physical and mechanical aspects that result in strong phase-separation (segregation). These include pressure gradients, volume fractions of solid and fluid phases and their gradients, shear-rates, flow depth, material friction, viscosity, material densities, boundary structures, gravity and topographic constraints, grain shape, size, etc. Due to the inherent separation mechanism, as the mass moves down slope, more and more solid particles are brought to the front, resulting in a solid-rich and mechanically strong frontal surge head followed by a weak tail largely consisting of the viscous fluid. The primary frontal surge head followed by secondary surge is the consequence of the phase-separation. Such typical and dominant phase-separation phenomena are revealed here for the first time in real two-phase debris flow modeling and simulations. However, these phenomena may depend on the bulk material composition and the applied forces. Reference: Pudasaini, Shiva P. (2012): A general two-phase debris flow model. J. Geophys. Res., 117, F03010, doi: 10.1029/2011JF002186.

Multiple fuel supply system for an internal combustion engine

DOEpatents

Crothers, William T.

1977-01-01

A multiple fuel supply or an internal combustion engine wherein phase separation of components is deliberately induced. The resulting separation permits the use of a single fuel tank to supply components of either or both phases to the engine. Specifically, phase separation of a gasoline/methanol blend is induced by the addition of a minor amount of water sufficient to guarantee separation into an upper gasoline phase and a lower methanol/water phase. A single fuel tank holds the two-phase liquid with separate fuel pickups and separate level indicators for each phase. Either gasoline or methanol, or both, can be supplied to the engine as required by predetermined parameters. A fuel supply system for a phase-separated multiple fuel supply contained in a single fuel tank is described.

A Temperature-Dependent Phase-Field Model for Phase Separation and Damage

NASA Astrophysics Data System (ADS)

Heinemann, Christian; Kraus, Christiane; Rocca, Elisabetta; Rossi, Riccarda

2017-07-01

In this paper we study a model for phase separation and damage in thermoviscoelastic materials. The main novelty of the paper consists in the fact that, in contrast with previous works in the literature concerning phase separation and damage processes in elastic media, in our model we encompass thermal processes, nonlinearly coupled with the damage, concentration and displacement evolutions. More particularly, we prove the existence of "entropic weak solutions", resorting to a solvability concept first introduced in Feireisl (Comput Math Appl 53:461-490, 2007) in the framework of Fourier-Navier-Stokes systems and then recently employed in Feireisl et al. (Math Methods Appl Sci 32:1345-1369, 2009) and Rocca and Rossi (Math Models Methods Appl Sci 24:1265-1341, 2014) for the study of PDE systems for phase transition and damage. Our global-in-time existence result is obtained by passing to the limit in a carefully devised time-discretization scheme.

High-performance liquid-chromatographic separation of subcomponents of antimycin-A

USGS Publications Warehouse

Abidi, S.L.

1988-01-01

Using a reversed-phase high-performance liquid chromatographic (HPLC) technique, a mixture of antimycins A was separated into eight hitherto unreported subcomponents, Ala, Alb, A2a, A2b, A3a, A3b, A4a, and A4b. Although a base-line resolution of the known four major antimycins Al, A2, A3, and A4 was readily achieved with mobile phases containing acetate buffers, the separation of the new antibiotic subcomponents was highly sensitive to variation in mobile phase conditions. The type and composition of organic modifiers, the nature of buffer salts, and the concentration of added electrolytes had profound effects on capacity factors, separation factors, and peak resolution values. Of the numerous chromatographic systems examined, a mobile phase consisting of methanol-water (70:30) and 0.005 M tetrabutylammonium phosphate at pH 3.0 yielded the most satisfactory results for the separation of the subcomponents. Reversed-phase gradient HPLC separation of the dansylated or methylated antibiotic compounds produced superior chromatographic characteristics and the presence of added electrolytes was not a critical factor for achieving separation. Differences in the chromatographic outcome between homologous and structural isomers were interpretated based on a differential solvophobic interaction rationale. Preparative reversed-phase HPLC under optimal conditions enabled isolation of pure samples of the methylated antimycin subcomponents for use in structural studies.

Texas A&M vortex type phase separator

NASA Astrophysics Data System (ADS)

Best, Frederick

2000-01-01

Phase separation is required for regenerative biological and chemical process systems as well as thermal transport and rejection systems. Liquid and gas management requirements for future spacecraft will demand small, passive systems able to operate over wide ranges of inlet qualities. Conservation and recycling of air and water is a necessary part of the construction and operation of the International Space Station as well as future long duration space missions. Space systems are sensitive to volume, mass, and power. Therefore, it is necessary to develop a method to recycle wastewater with minimal power consumption. Regenerative life support systems currently being investigated require phase separation to separate the liquid from the gas produced. The microgravity phase separator designed and fabricated at Texas A&M University relies on centripetal driven buoyancy forces to form a gas-liquid vortex within a fixed, right-circular cylinder. Two-phase flow is injected tangentially along the inner wall of this cylinder producing a radial acceleration gradient. The gradient produced from the intrinsic momentum of the injected mixture results in a rotating flow that drives the buoyancy process by the production of a hydrostatic pressure gradient. Texas A&M has flown several KC-135 flights with separator. These flights have included scaling studies, stability and transient investigations, and tests for inventory instrumentation. Among the hardware tested have been passive devices for separating mixed vapor/liquid streams into single-phase streams of vapor only and liquid only. .

Phase-separation induced extraordinary toughening of magnetic hydrogels

NASA Astrophysics Data System (ADS)

Tang, Jingda; Li, Chenghai; Li, Haomin; Lv, Zengyao; Sheng, Hao; Lu, Tongqing; Wang, T. J.

2018-05-01

Phase separation markedly influences the physical properties of hydrogels. Here, we find that poly (N, N-dimethylacrylamide) (PDMA) hydrogels suffer from phase separation in aqueous sodium hydroxide solutions when the concentration is higher than 2 M. The polymer volume fraction and mechanical properties show an abrupt change around the transition point. We utilize this phase separation mechanism to synthesize tough magnetic PDMA hydrogels with the in-situ precipitation method. For comparison, we also prepared magnetic poly (2-acrylamido-2-methyl-propane sulfonic acid sodium) (PNaAMPS) magnetic hydrogels, where no phase separation occurs. The phase-separated magnetic PDMA hydrogels exhibit an extraordinarily high toughness of ˜1000 J m-2; while non-phase-separated magnetic PNaAMPS hydrogels only show a toughness of ˜1 J m-2, three orders of magnitude lower than that of PDMA hydrogels. This phase separation mechanism may become a new approach to prepare tough magnetic hydrogels and inspire more applications.

Hydrogen isotope systematics of phase separation in submarine hydrothermal systems: Experimental calibration and theoretical models

USGS Publications Warehouse

Berndt, M.E.; Seal, R.R.; Shanks, Wayne C.; Seyfried, W.E.

1996-01-01

Hydrogen isotope fractionation factors were measured for coexisting brines and vapors formed by phase separation of NaCl/H2O fluids at temperatures ranging from 399-450??C and pressures from 277-397 bars. It was found that brines are depleted in D compared to coexisting vapors at all conditions studied. The magnitude of hydrogen isotope fractionation is dependent on the relative amounts of Cl in the two phases and can be empirically correlated to pressure using the following relationship: 1000 ln ??(vap-brine) = 2.54(??0.83) + 2.87(??0.69) x log (??P), where ??(vap-brine) is the fractionation factor and ??P is a pressure term representing distance from the critical curve in the NaCl/H2O system. The effect of phase separation on hydrogen isotope distribution in subseafloor hydrothermal systems depends on a number of factors, including whether phase separation is induced by heating at depth or by decompression of hydrothermal fluids ascending to the seafloor. Phase separation in most subseafloor systems appears to be a simple process driven by heating of seawater to conditions within the two-phase region, followed by segregation and entrainment of brine or vapor into a seawater dominated system. Resulting vent fluids exhibit large ranges in Cl concentration with no measurable effect on ??D. Possible exceptions to this include hydrothermal fluids venting at Axial and 9??N on the East Pacific Rise. High ??D values of low Cl fluids venting at Axial are consistent with phase separation taking place at relatively shallow levels in the oceanic crust while negative ??D values in some low Cl fluids venting at 9??N suggest involvement of a magmatic fluid component or phase separation of D-depleted brines derived during previous hydrothermal activity.

Phase-separated, epitaxial composite cap layers for electronic device applications and method of making the same

DOEpatents

Aytug, Tolga [Knoxville, TN; Paranthaman, Mariappan Parans [Knoxville, TN; Polat, Ozgur [Knoxville, TN

2012-07-17

An electronic component that includes a substrate and a phase-separated layer supported on the substrate and a method of forming the same are disclosed. The phase-separated layer includes a first phase comprising lanthanum manganate (LMO) and a second phase selected from a metal oxide (MO), metal nitride (MN), a metal (Me), and combinations thereof. The phase-separated material can be an epitaxial layer and an upper surface of the phase-separated layer can include interfaces between the first phase and the second phase. The phase-separated layer can be supported on a buffer layer comprising a composition selected from the group consisting of IBAD MgO, LMO/IBAD-MgO, homoepi-IBAD MgO and LMO/homoepi-MgO. The electronic component can also include an electronically active layer supported on the phase-separated layer. The electronically active layer can be a superconducting material, a ferroelectric material, a multiferroic material, a magnetic material, a photovoltaic material, an electrical storage material, and a semiconductor material.

Multi-mode application of graphene quantum dots bonded silica stationary phase for high performance liquid chromatography.

PubMed

Wu, Qi; Sun, Yaming; Zhang, Xiaoli; Zhang, Xia; Dong, Shuqing; Qiu, Hongdeng; Wang, Litao; Zhao, Liang

2017-04-07

Graphene quantum dots (GQDs), which possess hydrophobic, hydrophilic, π-π stacking and hydrogen bonding properties, have great prospect in HPLC. In this study, a novel GQDs bonded silica stationary phase was prepared and applied in multiple separation modes including normal phase, reversed phase and hydrophilic chromatography mode. Alkaloids, nucleosides and nucleobases were chosen as test compounds to evaluate the separation performance of this column in hydrophilic chromatographic mode. The tested polar compounds achieved baseline separation and the resolutions reached 2.32, 4.62, 7.79, 1.68 for thymidine, uridine, adenosine, cytidine and guanosine. This new column showed satisfactory chromatographic performance for anilines, phenols and polycyclic aromatic hydrocarbons in normal and reversed phase mode. Five anilines were completely separated within 10min under the condition of mobile phase containing only 10% methanol. The effect of water content, buffer concentration and pH on chromatographic separation was further investigated, founding that this new stationary phase showed a complex retention mechanism of partitioning, adsorption and electrostatic interaction in hydrophilic chromatography mode, and the multiple retention interactions such as π-π stacking and π-π electron-donor-acceptor interaction played an important role during the separation process. This GQDs bonded column, which allows us to adjust appropriate chromatography mode according to the properties of analytes, has possibility in actual application after further research. Copyright © 2017 Elsevier B.V. All rights reserved.

Reversed-phase thin-layer chromatography of homologs of Antimycin-A and related derivatives

USGS Publications Warehouse

Abidi, Sharon L.

1989-01-01

Using a reversed-phase high-performance liquid chromatographic (HPLC) technique, a mixture of antimycins A was separated into eight hitherto unreported subcomponents, Ala, Alb, A2a, A2b, A3a, A3b, A4a, and A4b. Although a base-line resolution of the known four major antimycins Al, A2, A3, and A4 was readily achieved with mobile phases containing acetate buffers, the separation of the new antibiotic subcomponents was highly sensitive to variation in mobile phase conditions. The type and composition of organic modifiers, the nature of buffer salts, and the concentration of added electrolytes had profound effects on capacity factors, separation factors, and peak resolution values. Of the numerous chromatographic systems examined, a mobile phase consisting of methanol-water (70:30) and 0.005 M tetrabutylammonium phosphate at pH 3.0 yielded the most satisfactory results for the separation of the subcomponents. Reversed-phase gradient HPLC separation of the dansylated or methylated antibiotic compounds produced superior chromatographic characteristics and the presence of added electrolytes was not a critical factor for achieving separation. Differences in the chromatographic outcome between homologous and structural isomers were interpretated based on a differential solvophobic interaction rationale. Preparative reversed-phase HPLC under optimal conditions enabled isolation of pure samples of the methylated antimycin subcomponents for use in structural studies.

Investigation of phase separated polyimide blend films containing boron nitride using FTIR imaging

NASA Astrophysics Data System (ADS)

Chae, Boknam; Hong, Deok Gi; Jung, Young Mee; Won, Jong Chan; Lee, Seung Woo

2018-04-01

Immiscible aromatic polyimide (PI) blend films and a PI blend film incorporated with thermally conductive boron nitride (BN) were prepared, and their phase separation behaviors were examined by optical microscopy and FTIR imaging. The 2,2‧-bis(trifluoromethyl)benzidine (TFMB)-containing and 4,4‧-thiodianiline (TDA)-containing aromatic PI blend films and a PI blend/BN composite film show two clearly separated regions; one region is the TFMB-rich phase, and the other region is the TDA-rich phase. The introduction of BN induces morphological changes in the immiscible aromatic PI blend film without altering the composition of either domain. In particular, the BN is selectively incorporated into the TDA-rich phase in this study.

STS-42 Phase Partitioning Experiment (PPE) closeup taken onboard OV-103

NASA Technical Reports Server (NTRS)

1992-01-01

STS-42 Phase Partitioning Experiment (PPE), an International Microgravity Laboratory 1 (IML-1) experiment, is documented in a closeup taken onboard Discovery, Orbiter Vehicle (OV) 103. Phase partitioning is a very effective technique used by biochemists and cell biologists to obtain fairly pure cells. Cells are separated and collected in a mixture of two immiscible liquids (fluids that tend not to mix) by their surface characteristics. In the PPE, investigators feel they will be able to separate closely related cells because cell density and convection flows are not factors in the phase partitioning process in space. They also hope to study other factors that influence the process. Phase partitioning is used to separate biological materials such as bone marrow cells for cancer treatment.

Intrinsic crystal phase separation in the antiferromagnetic superconductor Rb(y)Fe(2-x)Se2: a diffraction study.

PubMed

Yu Pomjakushin, V; Krzton-Maziopa, A; Pomjakushina, E V; Conder, K; Chernyshov, D; Svitlyk, V; Bosak, A

2012-10-31

The crystal and magnetic structures of the superconducting iron-based chalcogenides Rb(y)Fe(2-x)Se(2) have been studied by means of single-crystal synchrotron x-ray and high-resolution neutron powder diffraction in the temperature range 2-570 K. The ground state of the crystal is an intrinsically phase-separated state with two distinct-by-symmetry phases. The main phase has the iron vacancy ordered √5 × √5 superstructure (I4/m space group) with AFM ordered Fe spins. The minority phase does not have √5 × √5-type of ordering and has a smaller in-plane lattice constant a and larger tetragonal c-axis and can be well described by assuming the parent average vacancy disordered structure (I4/mmm space group) with the refined stoichiometry Rb(0.60(5))(Fe(1.10(5))Se)(2). The minority phase amounts to 8-10% mass fraction. The unit cell volume of the minority phase is 3.2% smaller than the one of the main phase at T = 2 K and has quite different temperature dependence. The minority phase merges with the main vacancy ordered phase on heating above the phase separation temperature T(P) = 475 K. The spatial dimensions of the phase domains strongly increase above T(P) from 1000 to >2500 Å due to the integration of the regions of the main phase that were separated by the second phase at low temperatures. Additional annealing of the crystals at a temperature T = 488 K, close to T(P), for a long time drastically reduces the amount of the minority phase.

Architecture Study on Telemetry Coverage for Immediate Post-Separation Phase

NASA Technical Reports Server (NTRS)

Cheung, Kar-Ming; Lee, Charles H.; Kellogg, Kent H.; Stocklin, Frank J.; Zillig, David J.; Fielhauer, Karl B.

2008-01-01

This paper presents the preliminary results of an architecture study that provides continuous telemetry coverage for NASA missions for immediate post-separation phase. This study is a collaboration effort between Jet Propulsion Laboratory (JPL), Goddard Space Flight Center (GSFC), and Applied Physics Laboratory (APL). After launch when the spacecraft separated from the upper stage, the spacecraft typically executes a number of mission-critical operations prior to the deployment of solar panels and the activation of the primary communication subsystem. JPL, GSFC, and APL have similar design principle statements that require continuous coverage of mission-critical telemetry during the immediate post-separation phase. To conform to these design principles, an architecture that consists of a separate spacecraft transmitter and a robust communication network capable of tracking the spacecraft signals is needed.This paper presents the preliminary results of an architecture study that provides continuous telemetry coverage for NASA missions for immediate post-separation phase. This study is a collaboration effort between Jet Propulsion Laboratory (JPL), Goddard Space Flight Center (GSFC), and Applied Physics Laboratory (APL). After launch when the spacecraft separated from the upper stage, the spacecraft typically executes a number of mission-critical operations prior to the deployment of solar panels and the activation of the primary communication subsystem. JPL, GSFC, and APL have similar design principle statements that require continuous coverage of mission-critical telemetry during the immediate post-separation phase. To conform to these design principles, an architecture that consists of a separate spacecraft transmitter and a robust communication network capable of tracking the spacecraft signals is needed. The main results of this study are as follows: 1) At low altitude (< 10000 km) when most post-separation critical operations are executed, Earth-based network (e.g. Deep Space Network (DSN)) can only provide limited coverage, whereas space-based network (e.g. Space Network (SN)) can provide continuous coverage. 2) Commercial-off-the-shelf SN compatible transmitters are available for small satellite applications. In this paper we present the detailed coverage analysis of Earth-based and Space-based networks. We identify the key functional and performance requirements of the architecture, and describe the proposed selection criteria of the spacecraft transmitter. We conclude the paper with a proposed forward plan.

Effects of temperature and solvent condition on phase separation induced molecular fractionation of gum arabic/hyaluronan aqueous mixtures.

PubMed

Hu, Bing; Han, Lingyu; Gao, Zhiming; Zhang, Ke; Al-Assaf, Saphwan; Nishinari, Katsuyoshi; Phillips, Glyn O; Yang, Jixin; Fang, Yapeng

2018-05-14

Effects of temperature and solvent condition on phase separation-induced molecular fractionation of gum arabic/hyaluronan (GA/HA) mixed solutions were investigated. Two gum arabic samples (EM10 and STD) with different molecular weights and polydispersity indices were used. Phase diagrams, including cloud and binodal curves, were established by visual observation and GPC-RI methods. The molecular parameters of control and fractionated GA, from upper and bottom phases, were measured by GPC-MALLS. Fractionation of GA increased the content of arabinogalactan-protein complex (AGP) from ca. 11% to 18% in STD/HA system and 28% to 55% in EM10/HA system. The phase separation-induced molecular fractionation was further studied as a function of temperature and solvent condition (varying ionic strength and ethanol content). Increasing salt concentration (from 0.5 to 5 mol/L) greatly reduced the extent of phase separation-induced fractionation. This effect may be ascribed to changes in the degree of ionization and shielding of the acid groups. Increasing temperature (from 4 °C to 80 °C) also exerted a significant influence on phase separation-induced fractionation. The best temperature for GA/HA mixture system was 40 °C while higher temperature negatively affected the fractionation due to denaturation and possibly degradation in mixed solutions. Increasing the ethanol content up to 30% showed almost no effect on the phase separation induced fractionation. Copyright © 2018 Elsevier B.V. All rights reserved.

Method for separating disparate components in a fluid stream

DOEpatents

Meikrantz, David H.

1990-01-01

The invention provides a method of separating a mixed component waste stream in a centrifugal separator. The mixed component waste stream is introduced into the separator and is centrifugally separated within a spinning rotor. A dual vortex separation occurs due to the phase density differences, with the phases exiting the rotor distinct from one another. In a preferred embodiment, aqueous solutions of organics can be separated with up to 100% efficiency. The relatively more dense water phase is centrifugally separated through a radially outer aperture in the separator, while the relatively less dense organic phase is separated through a radially inner aperture.

Kinetics of Polymer-Fullerene Phase Separation during Solvent Annealing Studied by Table-Top X-ray Scattering.

PubMed

Vegso, Karol; Siffalovic, Peter; Jergel, Matej; Nadazdy, Peter; Nadazdy, Vojtech; Majkova, Eva

2017-03-08

Solvent annealing is an efficient way of phase separation in polymer-fullerene blends to optimize bulk heterojunction morphology of active layer in polymer solar cells. To track the process in real time across all relevant stages of solvent evaporation, laboratory-based in situ small- and wide-angle X-ray scattering measurements were applied simultaneously to a model P3HT:PCBM blend dissolved in dichlorobenzene. The PCBM molecule agglomeration starts at ∼7 wt % concentration of solid content of the blend in solvent. Although PCBM agglomeration is slowed-down at ∼10 wt % of solid content, the rate constant of phase separation is not changed, suggesting agglomeration and reordering of P3HT molecular chains. Having the longest duration, this stage most affects BHJ morphology. Phase separation is accelerated rapidly at concentration of ∼25 wt %, having the same rate constant as the growth of P3HT crystals. P3HT crystallization is driving force for phase separation at final stages before a complete solvent evaporation, having no visible temporal overlap with PCBM agglomeration. For the first time, such a study was done in laboratory demonstrating potential of the latest generation table-top high-brilliance X-ray source as a viable alternative before more sophisticated X-ray scattering experiments at synchrotron facilities are performed.

Electronic Phase Separation in Iron Selenide (Li,Fe)OHFeSe Superconductor System

NASA Astrophysics Data System (ADS)

Mao, Yiyuan; Li, Jun; Huan, Yulong; Yuan, Jie; Li, Zi-an; Chai, Ke; Ma, Mingwei; Ni, Shunli; Tian, Jinpeng; Liu, Shaobo; Zhou, Huaxue; Zhou, Fang; Li, Jianqi; Zhang, Guangming; Jin, Kui; Dong, Xiaoli; Zhao, Zhongxian

2018-05-01

The phenomenon of phase separation into antiferromagnetic (AFM) and superconducting (SC) or normal-state regions has great implication for the origin of high-temperature (high-Tc) superconductivity. However, the occurrence of an intrinsic antiferromagnetism above the Tc of (Li, Fe)OHFeSe superconductor is questioned. Here we report a systematic study on a series of (Li, Fe)OHFeSe single crystal samples with Tc up to ~41 K. We observe an evident drop in the static magnetization at Tafm ~125 K, in some of the SC (Tc < ~38 K, cell parameter c < ~9.27 {\\AA}) and non-SC samples. We verify that this AFM signal is intrinsic to (Li, Fe)OHFeSe. Thus, our observations indicate mesoscopic-to-macroscopic coexistence of an AFM state with the normal (below Tafm) or SC (below Tc) state in (Li, Fe)OHFeSe. We explain such coexistence by electronic phase separation, similar to that in high-Tc cuprates and iron arsenides. However, such an AFM signal can be absent in some other samples of (Li, Fe)OHFeSe, particularly it is never observed in the SC samples of Tc > ~38 K, owing to a spatial scale of the phase separation too small for the macroscopic magnetic probe. For this case, we propose a microscopic electronic phase separation. It is suggested that the microscopic static phase separation reaches vanishing point in high-Tc (Li, Fe)OHFeSe, by the occurrence of two-dimensional AFM spin fluctuations below nearly the same temperature as Tafm reported previously for a (Li, Fe)OHFeSe (Tc ~42 K) single crystal. A complete phase diagram is thus established. Our study provides key information of the underlying physics for high-Tc superconductivity.

Effect of atomic disorder on the magnetic phase separation.

PubMed

Groshev, A G; Arzhnikov, A K

2018-05-10

The effect of disorder on the magnetic phase separation between the antiferromagnetic and incommensurate helical [Formula: see text] and [Formula: see text] phases is investigated. The study is based on the quasi-two-dimensional single-band Hubbard model in the presence of atomic disorder (the [Formula: see text] Anderson-Hubbard model). A model of binary alloy disorder is considered, in which the disorder is determined by the difference in energy between the host and impurity atomic levels at a fixed impurity concentration. The problem is solved within the theory of functional integration in static approximation. Magnetic phase diagrams are obtained as functions of the temperature, the number of electrons and impurity concentration with allowance for phase separation. It is shown that for the model parameters chosen, the disorder caused by impurities whose atomic-level energy is greater than that of the host atomic levels, leads to qualitative changes in the phase diagram of the impurity-free system. In the opposite case, only quantitative changes occur. The peculiarities of the effect of disorder on the phase separation regions of the quasi-two-dimensional Hubbard model are discussed.

Effect of atomic disorder on the magnetic phase separation

NASA Astrophysics Data System (ADS)

Groshev, A. G.; Arzhnikov, A. K.

2018-05-01

The effect of disorder on the magnetic phase separation between the antiferromagnetic and incommensurate helical and phases is investigated. The study is based on the quasi-two-dimensional single-band Hubbard model in the presence of atomic disorder (the Anderson–Hubbard model). A model of binary alloy disorder is considered, in which the disorder is determined by the difference in energy between the host and impurity atomic levels at a fixed impurity concentration. The problem is solved within the theory of functional integration in static approximation. Magnetic phase diagrams are obtained as functions of the temperature, the number of electrons and impurity concentration with allowance for phase separation. It is shown that for the model parameters chosen, the disorder caused by impurities whose atomic-level energy is greater than that of the host atomic levels, leads to qualitative changes in the phase diagram of the impurity-free system. In the opposite case, only quantitative changes occur. The peculiarities of the effect of disorder on the phase separation regions of the quasi-two-dimensional Hubbard model are discussed.

Specific features of the cathodoluminescence spectra of AlInGaN QWs, caused by the influence of phase separation and internal electric fields

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

Kuznetsova, Ya. V., E-mail: yana@mail.ioffe.ru; Jmerik, V. N.; Nechaev, D. V.

2016-07-15

The specific features of the cathodoluminescence (CL) spectra in AlInGaN heterostructures, caused by the influence of phase separation and internal electric fields, observed at varied CL excitation density, are studied. It is shown that the evolution of the CL spectrum and the variation in the spectral position of emission lines of nanoscale layers with current density in the primary electron beam makes it possible to identify the occurrence of phase separation in the layer and, in the absence of this separation, to estimate the electric-field strength in the active region of the structure.

A Laterally-Mobile Mixed Polymer/Polyelectrolyte Brush Undergoes a Macroscopic Phase Separation

NASA Astrophysics Data System (ADS)

Lee, Hoyoung; Park, Hae-Woong; Tsouris, Vasilios; Choi, Je; Mustafa, Rafid; Lim, Yunho; Meron, Mati; Lin, Binhua; Won, You-Yeon

2013-03-01

We studied mixed PEO and PDMAEMA brushes. The question we attempted to answer was: When the chain grafting points are laterally mobile, how will this lateral mobility influence the structure and phase behavior of the mixed brush? Two different model mixed PEO/PDMAEMA brush systems were prepared: a mobile mixed brush by spreading a mixture of two diblock copolymers, PEO-PnBA and PDMAEMA-PnBA, onto the air-water interface, and an inseparable mixed brush using a PEO-PnBA-PDMAEMA triblock copolymer having respective brush molecular weights matched to those of the diblock copolymers. These two systems were investigated by surface pressure-area isotherm, X-ray reflectivity and AFM imaging measurements. The results suggest that the mobile mixed brush undergoes a lateral macroscopic phase separation at high chain grafting densities, whereas the inseparable system is only microscopically phase separated under comparable brush density conditions. We also conducted an SCF analysis of the phase behavior of the mixed brush system. This analysis further supported the experimental findings. The macroscopic phase separation observed in the mobile system is in contrast to the microphase separation behavior commonly observed in two-dimensional laterally-mobile small molecule mixtures.

Hybrid films with phase-separated domains: A new class of functional materials

NASA Astrophysics Data System (ADS)

Kang, Minjee; Leal, Cecilia

The cell membrane is highly compartmentalized over micro-and nano scale. The compartmentalized domains play an important role in regulating the diffusion and distribution of species within and across the membrane. In this work, we introduced nanoscale heterogeneities into lipid films for the purpose of developing nature-mimicking phase-separated materials. The mixtures of phospholipids and amphiphilic block copolymers self-assemble into supported 1D multi-bilayers. We observed that in each lamella, mixtures of lipid and polymer phase-separate into domains that differ in their composition akin to sub-phases in cholesterol-containing lipid bilayers. Interestingly, we found evidence that like-domains are in registry across multilayers, making phase separation three-dimensional. To exploit such distinctive domain structure for surface-mediated drug delivery, we incorporated pharmaceutical molecules into the films. The drug release study revealed that the presence of domains in hybrid films modifies the diffusion pathways of drugs that become confined within phase-separated domains. A comprehensive domain structure coupled with drug diffusion pathways in films will be presented, offering new perspectives in designing a thin-film matrix system for controlled drug delivery. This work was supported by the National Science Foundation under Grant No. DMR-1554435.

Self-assembled structural color in nature

NASA Astrophysics Data System (ADS)

Parnell, Andrew

The vibrancy and variety of structural color found in nature has long been well-known; what has only recently been discovered is the sophistication of the physics that underlies these effects. In the talk I will discuss some of our recent studies of the structures responsible for color in bird feathers and beetle elytra, based on structural characterization using small angle x-ray scattering, x-ray tomography and optical modeling. These have enabled us to study a large number of structural color exhibiting materials and look for trends in the structures nature uses to provide these optical effects. In terms of creating the optical structure responsible for the color of the Eurasian Jay feathers (Garrulus glandarius) the nanostructure is produced by a phase-separation process that is arrested at a late stage; mastery of the color is achieved by control over the duration of this phase-separation process. Our analysis shows that nanostructure in single bird feather barbs can be varied continuously by controlling the time the keratin network is allowed to phase separate before mobility in the system is arrested. Dynamic scaling analysis of the single barb scattering data implies that the phase separation arrest mechanism is rapid and also distinct from the spinodal phase separation mechanism i.e. it is not gelation or intermolecular re-association. Any growing lengthscale using this spinodal phase separation approach must first traverse the UV and blue wavelength regions, growing the structure by coarsening, resulting in a broad distribution of domain sizes. AJP acknowledges financial support via the APS/DPOLY exchange lectureship 2017.

Microfluidic Droplet Dehydration for Concentrating Processes in Biomolecules

NASA Astrophysics Data System (ADS)

Anna, Shelley

2014-03-01

Droplets in microfluidic devices have proven useful as picoliter reactors for biochemical processing operations such as polymerase chain reaction, protein crystallization, and the study of enzyme kinetics. Although droplets are typically considered to be self-contained, constant volume reactors, there can be significant transport between the dispersed and continuous phases depending on solubility and other factors. In the present talk, we show that water droplets trapped within a microfluidic device for tens of hours slowly dehydrate, concentrating the contents encapsulated within. We use this slow dehydration along with control of the initial droplet composition to influence gellation, crystallization, and phase separation processes. By examining these concentrating processes in many trapped drops at once we gain insight into the stochastic nature of the events. In one example, we show that dehydration rate impacts the probability of forming a specific crystal habit in a crystallizing amino acid. In another example, we phase separate a common aqueous two-phase system within droplets and use the ensuing two phases to separate DNA from an initial mixture. We further influence wetting conditions between the two aqueous polymer phases and the continuous oil, promoting complete de-wetting and physical separation of the polymer phases. Thus, controlled dehydration of droplets allows for concentration, separation, and purification of important biomolecules on a chip.

A new approach to network heterogeneity: Polymerization Induced Phase Separation in photo-initiated, free-radical methacrylic systems

PubMed Central

Szczepanski, Caroline R.; Pfeifer, Carmem S.; Stansbury, Jeffrey W.

2012-01-01

Non-reactive, thermoplastic prepolymers (poly- methyl, ethyl and butyl methacrylate) were added to a model homopolymer matrix composed of triethylene glycol dimethacrylate (TEGDMA) to form heterogeneous networks via polymerization induced phase separation (PIPS). PIPS creates networks with distinct phase structure that can partially compensate for volumetric shrinkage during polymerization through localized internal volume expansion. This investigation utilizes purely photo-initiated, free-radical systems, broadening the scope of applications for PIPS since these processing conditions have not been studied previously. The introduction of prepolymer into TEGDMA monomer resulted in stable, homogeneous monomer formulations, most of which underwent PIPS upon photo-irradiation, creating heterogeneous networks. During polymerization the presence of prepolymer enhanced autoacceleration, allowing for a more extensive ambient cure of the material. Phase separation, as characterized by dynamic changes in sample turbidity, was monitored simultaneously with monomer conversion and either preceded or was coincident with network gelation. Dynamic mechanical analysis shows a broadening of the tan delta peak and secondary peak formation, characteristic of phase-separated materials, indicating one phase rich in prepolymer and another depleted form upon phase separation. In certain cases, PIPS leads to an enhanced physical reduction of volumetric shrinkage, which is attractive for many applications including dental composite materials. PMID:23109733

Antibody enhancement of free-flow electrophoresis

NASA Technical Reports Server (NTRS)

Cohly, H. H. P.; Morrison, Dennis R.; Atassi, M. Zouhair

1988-01-01

Specific T cell clones and antibodies (ABs) were developed to study the efficiency of purifying closely associated T cells using Continuous Flow Electrophoresis System. Enhanced separation is accomplished by tagging cells first with ABs directed against the antigenic determinants on the cell surface and then with ABs against the Fc portion of the first AB. This second AB protrudes sufficiently beyond the cell membrane and glycocalyx to become the major overall cell surface potential determinant and thus causes a reduction of electrophoretic mobility. This project was divided into three phases. Phase one included development of specific T cell clones and separation of these specific clones. Phase two extends these principles to the separation of T cells from spleen cells and immunized lymph node cells. Phase three applies this double antibody technique to the separation of T cytotoxic cells from bone marrow.

Shuttle unified navigation filter, revision 1

NASA Technical Reports Server (NTRS)

Muller, E. S., Jr.

1973-01-01

Equations designed to meet the navigation requirements of the separate shuttle mission phases are presented in a series of reports entitled, Space Shuttle GN and C Equation Document. The development of these equations is based on performance studies carried out for each particular mission phase. Although navigation equations have been documented separately for each mission phase, a single unified navigation filter design is embodied in these separate designs. The purpose of this document is to present the shuttle navigation equations in a form in which they would most likely be coded-as the single unified navigation filter used in each mission phase. This document will then serve as a single general reference for the navigation equations replacing each of the individual mission phase navigation documents (which may still be used as a description of a particular navigation phase).

Extraction of heavy metal (Ba, Sr) and high silica glass powder synthesis from waste CRT panel glasses by phase separation.

PubMed

Xing, Mingfei; Wang, Jingyu; Fu, Zegang; Zhang, Donghui; Wang, Yaping; Zhang, Zhiyuan

2018-04-05

In this study, a novel process for the extraction of heavy metal Ba and Sr from waste CRT panel glass and synchronous preparation of high silica glass powder was developed by glass phase separation. CRT panel glass was first remelted with B 2 O 3 under air atmosphere to produce alkali borosilicate glass. During the phase separation process, the glass separated into two interconnected phases which were B 2 O 3 -rich phase and SiO 2 -rich phase. Most of BaO, SrO and other metal oxides including Na 2 O, K 2 O, Al 2 O 3 and CaO were mainly concentrated in the B 2 O 3 -rich phase. The interconnected B 2 O 3 -rich phase can be completely leached out by 5mol/L HNO 3 at 90 ℃. The remaining SiO 2 -rich phase was porous glasses consisting almost entirely of silica. The maximum Ba and Sr removal rates were 98.84% and 99.38% and high silica glass powder (SiO 2 purity > 90 wt%) was obtained by setting the temperature, B 2 O 3 added amount and holding time at 1000-1100 ℃, 20-30% and 30 min, respectively. Thus this study developed an potential economical process for detoxification and reclamation of waste heavy metal glasses. Copyright © 2017 Elsevier B.V. All rights reserved.

Investigating the effect of V2O5 addition on sodium barium borosilicate glasses

NASA Astrophysics Data System (ADS)

Halder, Rumu; Sengupta, Pranesh; Sudarsan, V.; Kaushik, C. P.; Dey, G. K.

2016-05-01

V2O5 doped sodium barium borosilicate glasses were characterized by photoluminescence spectroscopy and electron probe microanalyzer (EPMA). The glass remains homogeneous for lower concentration of V2O5 but a phase separation is observed when V2O5 doping is increased beyond 5 mol%. Detailed microanalysis reveals that the phase separated glass consists of a phase containing V, Ba and Si and a separate Si rich phase within the glass matrix. The luminescence study demonstrated that at low concentration the vanadium mainly interacts with the structural units of B/Si while at higher concentrations, V-O-V/ V-O- Na+/Ba2+ linkages are formed.

Coherent and incoherent phase stabilities of thermoelectric rocksalt IV-VI semiconductor alloys

NASA Astrophysics Data System (ADS)

Doak, Jeff W.; Wolverton, C.

2012-10-01

Nanostructures formed by phase separation improve the thermoelectric figure of merit in lead chalcogenide semiconductor alloys, with coherent nanostructures giving larger improvements than incoherent nanostructures. However, large coherency strains in these alloys drastically alter the thermodynamics of phase stability. Incoherent phase stability can be easily inferred from an equilibrium phase diagram, but coherent phase stability is more difficult to assess experimentally. Therefore, we use density functional theory calculations to investigate the coherent and incoherent phase stability of the IV-VI rocksalt semiconductor alloy systems Pb(S,Te), Pb(Te,Se), Pb(Se,S), (Pb,Sn)Te, (Sn,Ge)Te, and (Ge,Pb)Te. Here we use the term coherent to indicate that there is a common and unbroken lattice between the phases under consideration, and we use the term incoherent to indicate that the lattices of coexisting phases are unconstrained and allowed to take on equilibrium volumes. We find that the thermodynamic ground state of all of the IV-VI pseudobinary systems studied is incoherent phase separation. We also find that the coherency strain energy, previously neglected in studies of these IV-VI alloys, is lowest along [111] (in contrast to most fcc metals) and is a large fraction of the thermodynamic driving force for incoherent phase separation in all systems. The driving force for coherent phase separation is significantly reduced, and we find that coherent nanostructures can only form at low temperatures where kinetics may prohibit their precipitation. Furthermore, by calculating the energies of ordered structures for these systems we find that the coherent phase stability of most IV-VI systems favors ordering over spinodal decomposition. Our results suggest that experimental reports of spinodal decomposition in the IV-VI rocksalt alloys should be re-examined.

Molecular-level characterization of crude oil compounds combining reversed-phase high-performance liquid chromatography with off-line high-resolution mass spectrometry

USGS Publications Warehouse

Sim, Arum; Cho, Yunju; Kim, Daae; Witt, Matthias; Birdwell, Justin E.; Kim, Byung Ju; Kim, Sunghwan

2014-01-01

A reversed-phase separation technique was developed in a previous study (Loegel et al., 2012) and successfully applied to the de-asphalted fraction of crude oil. However, to the best of our knowledge, the molecular-level characterization of oil fractions obtained by reversed-phase high-performance liquid chromatography (HPLC) coupled with high-resolution mass spectrometry (MS) has not yet been reported. A detailed characterization of the oil fractions prepared by reversed-phase HPLC was performed in this study. HPLC fractionation was carried out on conventional crude oil and an oil shale pyrolysate. The analyses of the fractions showed that the carbon number of alkyl chains and the double bond equivalent (DBE) value were the major factors determining elution order. The compounds with larger DBE (presumably more condensed aromatic structures) and smaller carbon number (presumably compounds with short side chains) were eluted earlier but those compounds with lower DBE values (presumably less aromatic structures) and higher carbon number (presumably compounds with longer alkyl chains) eluted later in the chromatograms. This separation behavior is in good agreement with that expected from the principles of reversed-phase separation. The data presented in this study show that reversed-phase chromatography is effective in separating crude oil compounds and can be combined with ultrahigh-resolution MS data to better understand natural oils and oil shale pyrolysates.

Film thickness dependence of phase separation and dewetting behaviors in PMMA/SAN blend films.

PubMed

You, Jichun; Liao, Yonggui; Men, Yongfeng; Shi, Tongfei; An, Lijia

2010-09-21

Film thickness dependence of complex behaviors coupled by phase separation and dewetting in blend [poly(methyl methacrylate) (PMMA) and poly(styrene-ran-acrylonitrile) (SAN)] films on silicon oxide substrate at 175 °C was investigated by grazing incidence ultrasmall-angle X-ray scattering (GIUSAX) and in situ atomic force microscopy (AFM). It was found that the dewetting pathway was under the control of the parameter U(q0)/E, which described the initial amplitude of the surface undulation and original thickness of film, respectively. Furthermore, our results showed that interplay between phase separation and dewetting depended crucially on film thickness. Three mechanisms including dewetting-phase separation/wetting, dewetting/wetting-phase separation, and phase separation/wetting-pseudodewetting were discussed in detail. In conclusion, it is relative rates of phase separation and dewetting that dominate the interplay between them.

Synthesis and evaluation of a maltose-bonded silica gel stationary phase for hydrophilic interaction chromatography and its application in Ginkgo Biloba extract separation in two-dimensional systems.

PubMed

Sheng, Qianying; Yang, Kaiya; Ke, Yanxiong; Liang, Xinmiao; Lan, Minbo

2016-09-01

Maltose covalently bonded to silica was prepared by using carbonyl diimidazole as a cross-linker and employed as a stationary phase for hydrophilic interaction liquid chromatography. The column efficiency and the effect of water content, buffer concentration, and pH value influenced on retention were investigated. The separation or enrichment selectivity was also studied with nucleosides, saccharides, amino acids, peptides, and glycopeptides. The results indicated that the stationary phase processed good separation efficiency and separation selectivity in hydrophilic interaction liquid chromatography mode. Moreover, a two-dimensional hydrophilic interaction liquid chromatography× reversed-phase liquid chromatography method with high orthogonality was developed to analyze the Ginkgo Biloba extract fractions. The development of this two-dimensional chromatographic system would be an effective tool for the separation of complex samples of different polarities and contents. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Crosslinked structurally-tuned polymeric ionic liquids as stationary phases for the analysis of hydrocarbons in kerosene and diesel fuels by comprehensive two-dimensional gas chromatography.

PubMed

Zhang, Cheng; Park, Rodney A; Anderson, Jared L

2016-04-01

Structurally-tuned ionic liquids (ILs) have been previously applied as the second dimension column in comprehensive two-dimensional gas chromatography (GC×GC) and have demonstrated high selectivity in the separation of individual aliphatic hydrocarbons from other aliphatic hydrocarbons. However, the maximum operating temperatures of these stationary phases limit the separation of analytes with high boiling points. In order to address this issue, a series of polymeric ionic liquid (PIL)-based stationary phases were prepared in this study using imidazolium-based IL monomers via in-column free radical polymerization. The IL monomers were functionalized with long alkyl chain substituents to provide the needed selectivity for the separation of aliphatic hydrocarbons. Columns were prepared with different film thicknesses to identify the best performing stationary phase for the separation of kerosene. The bis[(trifluoromethyl)sulfonyl]imide ([NTf2](-))-based PIL stationary phase with larger film thickness (0.28μm) exhibited higher selectivity for aliphatic hydrocarbons and showed a maximum allowable operating temperature of 300°C. PIL-based stationary phases containing varied amount of IL-based crosslinker were prepared to study the effect of the crosslinker on the selectivity and thermal stability of the resulting stationary phase. The optimal resolution of aliphatic hydrocarbons was achieved when 50% (w/w) of crosslinker was incorporated into the PIL-based stationary phase. The resulting stationary phase exhibited good selectivity for different groups of aliphatic hydrocarbons even after being conditioned at 325°C. Finally, the crosslinked PIL-based stationary phase was compared with SUPELCOWAX 10 and DB-17 columns for the separation of aliphatic hydrocarbons in diesel fuel. Better resolution of aliphatic hydrocarbons was obtained when employing the crosslinked PIL-based stationary phase as the second dimension column. Copyright © 2016 Elsevier B.V. All rights reserved.

Sample selection and testing of separation processes

NASA Technical Reports Server (NTRS)

Karr, L. J.

1985-01-01

Phase partitioning, which has become an important tool for the separation and purification of biological materials, was studied. Instruments available for this technique were researched and a countercurrent distribution apparatus, the Biosheff MK2N, was purchased. Various proteins, polysaccharides and cells were studied as models to determine operating procedures and conditions for this piece of equipment. Results were compared with those obtained from other similar equipment, including a nonsynchronous coil planet centrifuge device. Additionally, work was done with affinity ligands attached to PEG, which can further enhance the separation capabilities of phase partitioning.

Phase separation of in situ forming poly (lactide-co-glycolide acid) implants investigated using a hydrogel-based subcutaneous tissue surrogate and UV-vis imaging.

PubMed

Sun, Yu; Jensen, Henrik; Petersen, Nickolaj J; Larsen, Susan W; Østergaard, Jesper

2017-10-25

Phase separation of in situ forming poly (lactide-co-glycolide acid) (PLGA) implants with agarose hydrogels as the provider of nonsolvent (water) mimicking subcutaneous tissue was investigated using a novel UV-vis imaging-based analytical platform. In situ forming implants of PLGA-1-methyl-2-pyrrolidinone and PLGA-triacetin representing fast and slow phase separating systems, respectively, were evaluated using this platform. Upon contact with the agarose hydrogel, the phase separation of the systems was followed by the study of changes in light transmission and absorbance as a function of time and position. For the PLGA-1-methyl-2-pyrrolidinone system, the rate of spatial phase separation was determined and found to decrease with increasing the PLGA concentration from 20% to 40% (w/w). Hydrogels with different agarose concentrations (1% and 10% (w/v)) were prepared for providing the nonsolvent, water, to the in situ forming PLGA implants simulating the injection site environment. The resulting implant morphology depended on the stiffness of hydrogel matrix, indicating that the matrix in which implants are formed is of importance. Overall, the work showed that the UV-vis imaging-based platform with an agarose hydrogel mimicking the subcutaneous tissue holds potential in providing bio-relevant and mechanistic information on the phase separation processes of in situ forming implants. Copyright © 2017 Elsevier B.V. All rights reserved.

Gradient enhanced-fluidity liquid hydrophilic interaction chromatography of ribonucleic acid nucleosides and nucleotides: A "green" technique.

PubMed

Beilke, Michael C; Beres, Martin J; Olesik, Susan V

2016-03-04

A "green" hydrophilic interaction liquid chromatography (HILIC) technique for separating the components of mixtures with a broad range of polarities is illustrated using enhanced-fluidity liquid mobile phases. Enhanced-fluidity liquid chromatography (EFLC) involves the addition of liquid CO2 to conventional liquid mobile phases. Decreased mobile phase viscosity and increased analyte diffusivity results when a liquefied gas is dissolved in common liquid mobile phases. The impact of CO2 addition to a methanol:water (MeOH:H2O) mobile phase was studied to optimize HILIC gradient conditions. For the first time a fast separation of 16 ribonucleic acid (RNA) nucleosides/nucleotides was achieved (16min) with greater than 1.3 resolution for all analyte pairs. By using a gradient, the analysis time was reduced by over 100% compared to similar separations conducted under isocratic conditions. The optimal separation using MeOH:H2O:CO2 mobile phases was compared to MeOH:H2O and acetonitrile:water (ACN:H2O) mobile phases. Based on chromatographic performance parameters (efficiency, resolution and speed of analysis) and an assessment of the environmental impact of the mobile phase mixtures, MeOH:H2O:CO2 mixtures are preferred over ACN:H2O or MeOH:H2O mobile phases for the separation of mixtures of RNA nucleosides and nucleotides. Copyright © 2016 Elsevier B.V. All rights reserved.

Identifying Effective Design Approaches to Allocate Genotypes in Two-Phase Designs: A Case Study in Pelargonium zonale

PubMed Central

Molenaar, Heike; Boehm, Robert; Piepho, Hans-Peter

2018-01-01

Robust phenotypic data allow adequate statistical analysis and are crucial for any breeding purpose. Such data is obtained from experiments laid out to best control local variation. Additionally, experiments frequently involve two phases, each contributing environmental sources of variation. For example, in a former experiment we conducted to evaluate production related traits in Pelargonium zonale, there were two consecutive phases, each performed in a different greenhouse. Phase one involved the propagation of the breeding strains to obtain the stem cutting count, and phase two involved the assessment of root formation. The evaluation of the former study raised questions regarding options for improving the experimental layout: (i) Is there a disadvantage to using exactly the same design in both phases? (ii) Instead of generating a separate layout for each phase, can the design be optimized across both phases, such that the mean variance of a pair-wise treatment difference (MVD) can be decreased? To answer these questions, alternative approaches were explored to generate two-phase designs either in phase-wise order (Option 1) or across phases (Option 2). In Option 1 we considered the scenarios (i) using in both phases the same experimental design and (ii) randomizing each phase separately. In Option 2, we considered the scenarios (iii) generating a single design with eight replicates and splitting these among the two phases, (iv) separating the block structure across phases by dummy coding, and (v) design generation with optimal alignment of block units in the two phases. In both options, we considered the same or different block structures in each phase. The designs were evaluated by the MVD obtained by the intra-block analysis and the joint inter-block–intra-block analysis. The smallest MVD was most frequently obtained for designs generated across phases rather than for each phase separately, in particular when both phases of the design were separated with a single pseudo-level. The joint optimization ensured that treatment concurrences were equally balanced across pairs, one of the prerequisites for an efficient design. The proposed alternative approaches can be implemented with any model-based design packages with facilities to formulate linear models for treatment and block structures. PMID:29354145

Demulsification of water/oil/solid emulsions by hollow-fiber membranes

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

Tirmizi, N.P.; Raghuraman, B.; Wiencek, J.

1996-05-01

The demulsification techniques investigated use preferential surface wetting to allow separation of oil and water phases in ultrafiltration and microfiltration membranes. A hydrophobic membrane allows the permeation of an oil phase at almost zero pressure and retains the water phase, even though the molecular weight of the water molecule (18) is much smaller than that of the oil molecule (198 for tetradecane, used in this study). Hydrophobic membranes having pore sizes from 0.02 to 0.2 {micro}m were tested for demulsification of water-in-oil emulsions and water/oil/solid mixtures. The dispersed (aqueous)-phase drop sizes ranged from 1 to 5 {micro}m. High separation rates,more » as well as good permeate quality, were obtained with microfiltration membranes. Water content of permeating oil was 32--830 ppm depending on operating conditions and interfacial properties. For emulsions with high surfactant content, simultaneous operation of a hydrophobic and hydrophilic membrane, or simultaneous membrane separation with electric demulsification was more efficient in obtaining complete phase separation.« less

Segregation in like-charged polyelectrolyte-surfactant mixtures can be precisely tuned via manipulation of the surfactant mass ratio.

PubMed

Wills, Peter W; Lopez, Sonia G; Burr, Jocelyn; Taboada, Pablo; Yeates, Stephen G

2013-04-09

In this study, we consider segregative phase separation in aqueous mixtures of quaternary ammonium surfactants didecyldimethylammonium chloride (DDQ) and alkyl (C12, 70%; C14 30%) dimethyl benzyl ammonium chloride (BAC) upon the addition of poly(diallyldimethylammonium) chloride (pDADMAC) as a function of both concentration and molecular weight. The nature of the surfactant type is dominant in determining the concentration at which separation into an upper essentially surfactant-rich phase and lower polyelectrolyte-rich phase is observed. However, for high-molecular-weight pDADMAC there is a clear indication of an additional depletion flocculation effect. When the BAC/DDQ ratio is tuned, the segregative phase separation point can be precisely controlled. We propose a phase separation mechanism for like-charged quaternary ammonium polyelectrolyte/surfactant/water mixtures induced by a reduction in the ionic atmosphere around the surfactant headgroup and possible ion pair formation. An additional polyelectrolyte-induced depletion flocculation effect was also observed.

De-vitrification of nanoscale phase-separated amorphous thin films in the immiscible copper-niobium system

NASA Astrophysics Data System (ADS)

Puthucode, A.; Devaraj, A.; Nag, S.; Bose, S.; Ayyub, P.; Kaufman, M. J.; Banerjee, R.

2014-05-01

Copper and niobium are mutually immiscible in the solid state and exhibit a large positive enthalpy of mixing in the liquid state. Using vapour quenching via magnetron co-sputter deposition, far-from equilibrium amorphous Cu-Nb films have been deposited which exhibit a nanoscale phase separation. Annealing these amorphous films at low temperatures (~200 °C) initiates crystallization via the nucleation and growth of primary nanocrystals of a face-centred cubic Cu-rich phase separated by the amorphous matrix. Interestingly, subsequent annealing at a higher temperature (>300 °C) leads to the polymorphic nucleation and growth of large spherulitic grains of a body-centred cubic Nb-rich phase within the retained amorphous matrix of the partially crystallized film. This sequential two-stage crystallization process has been investigated in detail by combining transmission electron microscopy [TEM] (including high-resolution TEM) and atom probe tomography studies. These results provide new insights into the crystallization behaviour of such unusual far-from equilibrium phase-separated metallic glasses in immiscible systems.

Moisture-Induced Amorphous Phase Separation of Amorphous Solid Dispersions: Molecular Mechanism, Microstructure, and Its Impact on Dissolution Performance.

PubMed

Chen, Huijun; Pui, Yipshu; Liu, Chengyu; Chen, Zhen; Su, Ching-Chiang; Hageman, Michael; Hussain, Munir; Haskell, Roy; Stefanski, Kevin; Foster, Kimberly; Gudmundsson, Olafur; Qian, Feng

2018-01-01

Amorphous phase separation (APS) is commonly observed in amorphous solid dispersions (ASD) when exposed to moisture. The objective of this study was to investigate: (1) the phase behavior of amorphous solid dispersions composed of a poorly water-soluble drug with extremely low crystallization propensity, BMS-817399, and PVP, following exposure to different relative humidity (RH), and (2) the impact of phase separation on the intrinsic dissolution rate of amorphous solid dispersion. Drug-polymer interaction was confirmed in ASDs at different drug loading using infrared (IR) spectroscopy and water vapor sorption analysis. It was found that the drug-polymer interaction could persist at low RH (≤75% RH) but was disrupted after exposure to high RH, with the advent of phase separation. Surface morphology and composition of 40/60 ASD at micro-/nano-scale before and after exposure to 95% RH were also compared. It was found that hydrophobic drug enriched on the surface of ASD after APS. However, for the 40/60 ASD system, the intrinsic dissolution rate of amorphous drug was hardly affected by the phase behavior of ASD, which may be partially attributed to the low crystallization tendency of amorphous BMS-817399 and enriched drug amount on the surface of ASD. Intrinsic dissolution rate of PVP decreased resulting from APS, leading to a lower concentration in the dissolution medium, but supersaturation maintenance was not anticipated to be altered after phase separation due to the limited ability of PVP to inhibit drug precipitation and prolong the supersaturation of drug in solution. This study indicated that for compounds with low crystallization propensity and high hydrophobicity, the risk of moisture-induced APS is high but such phase separation may not have profound impact on the drug dissolution performance of ASDs. Therefore, application of ASD technology on slow crystallizers could incur low risks not only in physical stability but also in dissolution performance. Copyright © 2018 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.

Effect of Excipients on Liquid-Liquid Phase Separation and Aggregation in Dual Variable Domain Immunoglobulin Protein Solutions.

PubMed

Raut, Ashlesha S; Kalonia, Devendra S

2016-03-07

Liquid-liquid phase separation (LLPS) and aggregation can reduce the physical stability of therapeutic protein formulations. On undergoing LLPS, the protein-rich phase can promote aggregation during storage due to high concentration of the protein. Effect of different excipients on aggregation in protein solution is well documented; however data on the effect of excipients on LLPS is scarce in the literature. In this study, the effect of four excipients (PEG 400, Tween 80, sucrose, and hydroxypropyl beta-cyclodextrin (HPβCD)) on liquid-liquid phase separation and aggregation in a dual variable domain immunoglobulin protein solution was investigated. Sucrose suppressed both LLPS and aggregation, Tween 80 had no effect on either, and PEG 400 increased LLPS and aggregation. Attractive protein-protein interactions and liquid-liquid phase separation decreased with increasing concentration of HPβCD, indicating its specific binding to the protein. However, HPβCD had no effect on the formation of soluble aggregates and fragments in this study. LLPS and aggregation are highly temperature dependent; at low temperature protein exhibits LLPS, at high temperature protein exhibits aggregation, and at an intermediate temperature both phenomena occur simultaneously depending on the solution conditions.

The separation of flavonoids from Pongamia pinnata using combination columns in high-speed counter-current chromatography with a three-phase solvent system.

PubMed

Yin, Hao; Zhang, Si; Long, Lijuan; Yin, Hang; Tian, Xinpeng; Luo, Xiongming; Nan, Haihan; He, Sha

2013-11-08

The mangrove plant Pongamia pinnata (Leguminosae) is well known as a plant pesticide. Previous studies have indicated that the flavonoids are responsible of the biological activities of the plant. A new high-speed counter-current chromatography (HSCCC) method for the separation of three flavonoids, karanjin (1), pinnatin (2), and pongaflavone (3), from P. pinnata was developed in the present study. The lower and intermediate phase (LP and IP) of a new three-phase solvent system, n-hexane-acetonitrile-dichloromethane-water, at a volume ratio of 5:5:1:5, were used as the stationary phases, while the upper phase (UP) was used as the mobile phase, and the volume ratio between the stationary phases in the CCC column could be tuned by varying the initial pumped volume ratio of the stationary phases. The CCC columns containing all three phases of the solvent system were considered combination columns. According to the theories of combination column, it is possible to optimize the retention time of the target compounds by varying the volume ratio of the stationary phases in the HSCCC combination columns, as well as the suitable volume ratios of the stationary phases for the separation of the target compounds were predicted from the partition coefficients of the compounds in the three-phase solvent system. Then, three HSCCC separations using the combination columns with initial pumped LP:IP volume ratios of 1:0, 0.9:0.1, and 0.7:0.3 were performed separately based on the prediction. Three target compounds were prepared with high purity when the initial pumped volume ratio of the stationary phases was 0.9:0.1. The baseline separation of compounds 2 and 3 was achieved on the combination column with an initial pumped volume ratio of 0.7:0.3. Furthermore, the three experiments clearly demonstrated that the retentions and resolutions of the target compounds increased with an increasing volume ratio of IP, which is consistent with the prediction for the retention times for the solutes on combination columns. The method proposed here reduces the need for solvent selection compared with the conventional method and may have broad potential applicability in the preparation of natural products. Copyright © 2013 Elsevier B.V. All rights reserved.

Synthesis of a mixed-model stationary phase derived from glutamine for HPLC separation of structurally different biologically active compounds: HILIC and reversed-phase applications.

PubMed

Aral, Tarık; Aral, Hayriye; Ziyadanoğulları, Berrin; Ziyadanoğulları, Recep

2015-01-01

A novel mixed-mode stationary phase was synthesised starting from N-Boc-glutamine, aniline and spherical silica gel (4 µm, 60 Å). The prepared stationary phase was characterized by IR and elemental analysis. The new stationary phase bears an embedded amide group into phenyl ring, highly polar a terminal amide group and non-polar groups (phenyl and alkyl groups). At first, this new mixed-mode stationary phase was used for HILIC separation of four nucleotides and five nucleosides. The effects of different separation conditions, such as pH value, mobile phase and temperature, on the separation process were investigated. The optimum separation for nucleotides was achieved using HILIC isocratic elution with aqueous mobile phase and acetonitrile with 20°C column temperature. Under these conditions, the four nucleotides could be separated and detected at 265 nm within 14 min. Five nucleosides were separated under HILIC isocratic elution with aqueous mobile phase containing pH=3.25 phosphate buffer (10mM) and acetonitrile with 20°C column temperature and detected at 265 nm within 14 min. Chromatographic parameters as retention factor, selectivity, theoretical plate number and peak asymmetry factor were calculated for the effect of temperature and water content in mobile phase on the separation process. The new column was also tested for nucleotides and nucleosides mixture and six analytes were separated in 10min. The chromatographic behaviours of these polar analytes on the new mixed-model stationary phase were compared with those of HILIC columns under similar conditions. Further, phytohormones and phenolic compounds were separated in order to see influence of the new stationary phase in reverse phase conditions. Eleven plant phytohormones were separated within 13 min using RP-HPLC gradient elution with aqueous mobile phase containing pH=2.5 phosphate buffer (10mM) and acetonitrile with 20°C column temperature and detected at 230 or 278 nm. The best separation conditions for seven phenolic compounds was also achieved using reversed-phase HPLC gradient elution with aqueous mobile phase containing pH=2.5 phosphate buffer (10mM) and acetonitrile with 20°C column temperature and seven phenolic compounds could be separated and detected at 230 nm within 16 min. Copyright © 2014 Elsevier B.V. All rights reserved.

3D FT-IR imaging spectroscopy of phase-separation in a poly(3-hydroxybutyrate)/poly(L-lactic acid) blend

Treesearch

Miriam Unger; Julia Sedlmair; Heinz W. Siesler; Carol Hirschmugl; Barbara Illman

2014-01-01

In the present study, 3D FT-IR spectroscopic imaging measurements were applied to study the phase separation of a poly(3-hydroxybutyrate) (PHB)/poly(L-lactic acid) (PLA) (50:50 wt.%) polymer blend film. While in 2D projection imaging the z-dependent information is overlapped, thereby complicating the analysis, FT-IR spectro-micro-tomography,...

Phase separation in artificial vesicles driven by light and curvature

NASA Astrophysics Data System (ADS)

Rinaldin, Melissa; Pomp, Wim; Schmidt, Thomas; Giomi, Luca; Kraft, Daniela; Physics of Life Processes Team; Soft; Bio Mechanics Collaboration; Self-Assembly in Soft Matter Systems Collaboration

The role of phase-demixing in living cells, leading to the lipid-raft hypothesis, has been extensively studied. Lipid domains of higher lipid chain order are proposed to regulate protein spatial organization. Giant Unilamellar Vesicles provide an artificial model to study phase separation. So far temperature was used to initiate the process. Here we introduce a new methodology based on the induction of phase separation by light. To this aim, the composition of the lipid membrane is varied by photo-oxidation of lipids. The control of the process gained by using light allowed us to observe vesicle shape fluctuations during phase-demixing. The presence of fluctuations near the critical mixing point resembles features of a critical process. We quantitatively analyze these fluctuations using a 2d elastic model, from which we can estimate the material parameters such as bending rigidity and surface tension, demonstrating the non-equilibrium critical behaviour. Finally, I will describe recent attempts toward tuning the membrane composition by controlling the vesicle curvature.

Interactions between coherent twin boundaries and phase transition of iron under dynamic loading and unloading

NASA Astrophysics Data System (ADS)

Wang, Kun; Chen, Jun; Zhang, Xueyang; Zhu, Wenjun

2017-09-01

Phase transitions and deformation twins are constantly reported in many BCC metals under high pressure, whose interactions are of fundamental importance to understand the strengthening mechanism of these metals under extreme conditions. However, the interactions between twins and phase transition in BCC metals remain largely unexplored. In this work, interactions between coherent twin boundaries and α ↔ ɛ phase transition of iron are investigated using both non-equilibrium molecular dynamics simulations and the nudged elastic band method. Mechanisms of both twin-assisted phase transition and reverse phase transition are studied, and orientation relationships between BCC and HCP phases are found to be ⟨"separators="|11 1 ¯ ⟩ B C C||⟨"separators="|1 ¯2 1 ¯ 0 ⟩ H C P and ⟨"separators="|1 1 ¯ 0 ⟩ B C C||⟨"separators="|0001 ⟩ H C P for both cases. The twin boundary corresponds to {"separators="|10 1 ¯ 0 } H C P after the phase transition. It is amazing that the reverse transition seems to be able to "memorize" and recover the initial BCC twins. The memory would be partly lost when plastic slips take place in the HCP phase before the reverse transition. In the recovered initial BCC twins, three major twin spacings are observed, which are well explained in terms of energy barriers of transition from the HCP phase to the BCC twin. Besides, the variant selection rule of the twin assisted phase transition is also discussed. The results of present work could be expected to give some clues for producing ultra-fine grain structures in materials exhibiting martensitic phase transition.

Modeling phase separation in mixtures of intrinsically-disordered proteins

NASA Astrophysics Data System (ADS)

Gu, Chad; Zilman, Anton

Phase separation in a pure or mixed solution of intrinsically-disordered proteins (IDPs) and its role in various biological processes has generated interest from the theoretical biophysics community. Phase separation of IDPs has been implicated in the formation of membrane-less organelles such as nucleoli, as well as in a mechanism of selectivity in transport through the nuclear pore complex. Based on a lattice model of polymers, we study the phase diagram of IDPs in a mixture and describe the selective exclusion of soluble proteins from the dense-phase IDP aggregates. The model captures the essential behaviour of phase separation by a minimal set of coarse-grained parameters, corresponding to the average monomer-monomer and monomer-protein attraction strength, as well as the protein-to-monomer size ratio. Contrary to the intuition that strong monomer-monomer interaction increases exclusion of soluble proteins from the dense IDP aggregates, our model predicts that the concentration of soluble proteins in the aggregate phase as a function of monomer-monomer attraction is non-monotonic. We corroborate the predictions of the lattice model using Langevin dynamics simulations of grafted polymers in planar and cylindrical geometries, mimicking various in-vivo and in-vitro conditions.

Steric Pressure among Membrane-Bound Polymers Opposes Lipid Phase Separation.

PubMed

Imam, Zachary I; Kenyon, Laura E; Carrillo, Adelita; Espinoza, Isai; Nagib, Fatema; Stachowiak, Jeanne C

2016-04-19

Lipid rafts are thought to be key organizers of membrane-protein complexes in cells. Many proteins that interact with rafts have bulky polymeric components such as intrinsically disordered protein domains and polysaccharide chains. Therefore, understanding the interaction between membrane domains and membrane-bound polymers provides insights into the roles rafts play in cells. Multiple studies have demonstrated that high concentrations of membrane-bound polymeric domains create significant lateral steric pressure at membrane surfaces. Furthermore, our recent work has shown that lateral steric pressure at membrane surfaces opposes the assembly of membrane domains. Building on these findings, here we report that membrane-bound polymers are potent suppressors of membrane phase separation, which can destabilize lipid domains with substantially greater efficiency than globular domains such as membrane-bound proteins. Specifically, we created giant vesicles with a ternary lipid composition, which separated into coexisting liquid ordered and disordered phases. Lipids with saturated tails and poly(ethylene glycol) (PEG) chains conjugated to their head groups were included at increasing molar concentrations. When these lipids were sparse on the membrane surface they partitioned to the liquid ordered phase. However, as they became more concentrated, the fraction of GUVs that were phase-separated decreased dramatically, ultimately yielding a population of homogeneous membrane vesicles. Experiments and physical modeling using compositions of increasing PEG molecular weight and lipid miscibility phase transition temperature demonstrate that longer polymers are the most efficient suppressors of membrane phase separation when the energetic barrier to lipid mixing is low. In contrast, as the miscibility transition temperature increases, longer polymers are more readily driven out of domains by the increased steric pressure. Therefore, the concentration of shorter polymers required to suppress phase separation decreases relative to longer polymers. Collectively, our results demonstrate that crowded, membrane-bound polymers are highly efficient suppressors of phase separation and suggest that the ability of lipid domains to resist steric pressure depends on both their lipid composition and the size and concentration of the membrane-bound polymers they incorporate.

Vacancy-mediated fcc/bcc phase separation in Fe1 -xNix ultrathin films

NASA Astrophysics Data System (ADS)

Menteş, T. O.; Stojić, N.; Vescovo, E.; Ablett, J. M.; Niño, M. A.; Locatelli, A.

2016-08-01

The phase separation occurring in Fe-Ni thin films near the Invar composition is studied by using high-resolution spectromicroscopy techniques and density functional theory calculations. Annealed at temperatures around 300 ∘C ,Fe0.70Ni0.30 films on W(110) break into micron-sized bcc and fcc domains with compositions in agreement with the bulk Fe-Ni phase diagram. Ni is found to be the diffusing species in forming the chemical heterogeneity. The experimentally determined energy barrier of 1.59 ±0.09 eV is identified as the vacancy formation energy via density functional theory calculations. Thus, the principal role of the surface in the phase separation process is attributed to vacancy creation without interstitials.

Demixing kinetics of phase separated polymer solutions in microgravity. [cell separation

NASA Technical Reports Server (NTRS)

Brooks, D. E.; Bamberger, S. B.; Harris, J. M.; Vanalstine, J.; Snyder, R. S.

1987-01-01

In preparation for performing cell partitioning in space the demixing behavior of aqueous two phase systems containing dextran and poly(ethylene glycol) in microgravity was modeled with an isopycnic system and studied on aircraft flights and on STS 51-D. In all types of experiments demixing occurs, eventually producing one phase localized around the wall of the container with the other internalized within it. The demixing kinetics were analyzed in each case.

Charge pattern matching as a ‘fuzzy’ mode of molecular recognition for the functional phase separations of intrinsically disordered proteins

NASA Astrophysics Data System (ADS)

Lin, Yi-Hsuan; Brady, Jacob P.; Forman-Kay, Julie D.; Chan, Hue Sun

2017-11-01

Biologically functional liquid-liquid phase separation of intrinsically disordered proteins (IDPs) is driven by interactions encoded by their amino acid sequences. Little is currently known about the molecular recognition mechanisms for distributing different IDP sequences into various cellular membraneless compartments. Pertinent physics was addressed recently by applying random-phase-approximation (RPA) polymer theory to electrostatics, which is a major energetic component governing IDP phase properties. RPA accounts for charge patterns and thus has advantages over Flory-Huggins (FH) and Overbeek-Voorn mean-field theories. To make progress toward deciphering the phase behaviors of multiple IDP sequences, the RPA formulation for one IDP species plus solvent is hereby extended to treat polyampholyte solutions containing two IDP species plus solvent. The new formulation generally allows for binary coexistence of two phases, each containing a different set of volume fractions ({φ }1,{φ }2) for the two different IDP sequences. The asymmetry between the two predicted coexisting phases with regard to their {φ }1/{φ }2 ratios for the two sequences increases with increasing mismatch between their charge patterns. This finding points to a multivalent, stochastic, ‘fuzzy’ mode of molecular recognition that helps populate various IDP sequences differentially into separate phase compartments. An intuitive illustration of this trend is provided by FH models, whereby a hypothetical case of ternary coexistence is also explored. Augmentations of the present RPA theory with a relative permittivity {ɛ }{{r}}(φ ) that depends on IDP volume fraction φ ={φ }1+{φ }2 lead to higher propensities to phase separate, in line with the case with one IDP species we studied previously. Notably, the cooperative, phase-separation-enhancing effects predicted by the prescriptions for {ɛ }{{r}}(φ ) we deem physically plausible are much more prominent than that entailed by common effective medium approximations based on Maxwell Garnett and Bruggeman mixing formulas. Ramifications of our findings on further theoretical development for IDP phase separation are discussed.

Fast non-aqueous reversed-phase liquid chromatography separation of triacylglycerol regioisomers with isocratic mobile phase. Application to different oils and fats.

PubMed

Tamba Sompila, Arnaud W G; Héron, Sylvie; Hmida, Dorra; Tchapla, Alain

2017-01-15

The distribution of fatty acid species at the sn-1/3 position or the sn-2 position of triacylglycerols (TAGs) in natural fats and oils affects their physical and nutritional properties. In fats and oils, determining the presence of one or two regioisomers and the identification of structure, where they do have one, as well as their separation, became a problem of fundamental importance to solve. A variety of instrumental technics has been proposed, such as MS, chromatography-MS or pure chromatography. A number of studies deal with the optimization of the separation, but very often, they are expensive in time. In the present study, in order to decrease the analysis time while maintaining good chromatographic separation, we tested different monomeric and polymeric stationary phases and different chromatographic conditions (mobile phase composition and analysis temperature) using Non-Aqueous Reversed Phase Liquid Chromatography (NARP-LC). It was demonstrated that mixed polymeric stationary bonded silica with accessible terminal hydroxyl groups leads to very good separation for the pairs of TAGs regioisomers constituted by two saturated and one unsaturated fatty acid (with double bond number: from 1 to 6). A Nucleodur C18 ISIS percolated by isocratic mobile phase (acetonitrile/2-propanol) at 18°C leads to their separations in less than 15min. The difference of retention times between two regioisomers XYX and XXY are large enough to confirm, as application, the presence of POP, SOP, SOS and PLP and no PPO, SPO, SSO and PPL in Theobroma cacao butter. In the same way, this study respectively shows the presence of SOS, SOP and no SSO, PSO in Butyrospermum parkii butter, POP, SOP, SOS and no PPO, PSO and SSO in Carapa oil and finally POP and no PPO in Pistacia Lentiscus oil. Copyright © 2016 Elsevier B.V. All rights reserved.

Adhesive phase separation at the dentin interface under wet bonding conditions.

PubMed

Spencer, Paulette; Wang, Yong

2002-12-05

Under in vivo conditions, there is little control over the amount of water left on the tooth and, thus, there is the danger of leaving the dentin surface so wet that the bonding resin undergoes physical separation into hydrophobic and hydrophilic-rich phases. The purpose of this study was to investigate phase separation in 2,2-bis[4(2-hydroxy-3-methacryloyloxy-propyloxy)-phenyl] propane (BisGMA)-based adhesive using molecular microanalysis and to examine the effect of phase separation on the structural characteristics of the hybrid layer. Model BisGMA/HEMA (hydroxyethl methacrylate) mixtures with/without ethanol and commercial BisGMA-based adhesive (Single Bond) were combined with water at concentrations from 0 to 50 vol%. Macrophase separation in the BisGMA/HEMA/water mixtures was detected using cloud point measurements. In parallel with these measurements, the BisGMA/HEMA and adhesive/water mixtures were cast as films and polymerized. Molecular structure was recorded from the distinct features in the phase-separated adhesive using confocal Raman microspectroscopy (CRM). Human dentin specimens treated with Single Bond were analyzed with scanning electron microscopy (SEM) and CRM mapping across the dentin/adhesive interface. The model BisGMA/HEMA mixtures with ethanol and the commercial BisGMA-based adhesive experienced phase separation at approximately 25 vol% water. Raman spectra collected from the phase-separated adhesive indicated that the composition of the particles and surrounding matrix material was primarily BisGMA and HEMA, respectively. Based on SEM analysis, there was substantial porosity at the adhesive interface with dentin. Micro-Raman spectral analysis of the dentin/adhesive interface indicates that the contribution from the BisGMA component decreases by nearly 50% within the first micrometer. The morphologic results in corroboration with the spectroscopic data suggest that as a result of adhesive phase separation the hybrid layer is not an impervious 3-dimensional collagen/polymer network but a porous web characterized by hydrophobic BisGMA-rich particles distributed in a hydrophilic HEMA-rich matrix. Copyright 2002 Wiley Periodicals, Inc.

Stability of Mixed Preparations Consisting of Commercial Moisturizing Creams with an Ointment Base Investigated by Magnetic Resonance Imaging.

PubMed

Onuki, Yoshinori; Funatani, Chiaki; Yamamoto, Yoshihisa; Fukami, Toshiro; Koide, Tatsuo; Hayashi, Yoshihiro; Takayama, Kozo

2017-01-01

A moisturizing cream mixed with a steroid ointment is frequently prescribed to patients suffering from atopic dermatitis. However, there is a concern that the mixing operation causes destabilization. The present study was performed to investigate the stability of such preparations closely using magnetic resonance imaging (MRI). As sample preparations, five commercial moisturizing creams that are popular in Japan were mixed with an ointment base, a white petrolatum, at a volume ratio of 1 : 1. The mixed preparations were stored at 60°C to accelerate the destabilization processes. Subsequently, the phase separations induced by the storage test were monitored using MRI. Using advanced MR technologies including spin-spin relaxation time (T 2 ) mapping and MR spectroscopy, we successfully characterized the phase-separation behavior of the test samples. For most samples, phase separations developed by the bleeding of liquid oil components. From a sample consisting of an oil-in-water-type cream, Urepearl Cream 10%, a distinct phase-separation mode was observed, which was initiated by the aqueous component separating from the bottom part of the sample. The resultant phase separation was the most distinct among the test samples. To investigate the phase separation quantitatively and objectively, we conducted a histogram analysis on the acquired T 2 maps. The water-in-oil type creams were found to be much more stable after mixing with ointment base than those of oil-in-water type creams. This finding strongly supported the validity of the mixing operation traditionally conducted in pharmacies.

Effect of applied strain on phase separation of Fe-28 at.% Cr alloy: 3D phase-field simulation

NASA Astrophysics Data System (ADS)

Zhu, Lihui; Li, Yongsheng; Liu, Chengwei; Chen, Shi; Shi, Shujing; Jin, Shengshun

2018-04-01

A quantitative simulation of the separation of the α‧ phase in Fe-28 at.% Cr alloy under the effects of applied strain is performed by utilizing a three-dimensional phase-field model. The elongation of the Cr-enriched α‧ phase becomes obvious with the influence of applied uniaxial strain for the phase separation transforms from spinodal decomposition of 700 K to nucleation and growth of 773 K. The applied strain shows a significant influence on the early stage phase separation, and the influence is enlarged with the elevated temperature. The steady-state coarsening with the mechanism of spinodal decomposition is substantially affected by the applied strain for low-temperature aging, while the influence is reduced as the temperature increases and as the phase separation mechanism changes to nucleation and growth. The peak value of particle size distribution decreases, and the PSD for 773 K becomes more widely influenced by the applied strain. The simulation results of separation of the Cr-enriched α‧ phase with the applied strain provide a further understanding of the strain effect on the phase separation of Fe-Cr alloys from the metastable region to spinodal regions.

Electrospun Polymer Blend Nanofibers for Tunable Drug Delivery: The Role of Transformative Phase Separation on Controlling the Release Rate.

PubMed

Tipduangta, Pratchaya; Belton, Peter; Fábián, László; Wang, Li Ying; Tang, Huiru; Eddleston, Mark; Qi, Sheng

2016-01-04

Electrospun fibrous materials have a wide range of biomedical applications, many of them involving the use of polymers as matrices for incorporation of therapeutic agents. The use of polymer blends improves the tuneability of the physicochemical and mechanical properties of the drug loaded fibers. This also benefits the development of controlled drug release formulations, for which the release rate can be modified by altering the ratio of the polymers in the blend. However, to realize these benefits, a clear understanding of the phase behavior of the processed polymer blend is essential. This study reports an in depth investigation of the impact of the electrospinning process on the phase separation of a model partially miscible polymer blend, PVP K90 and HPMCAS, in comparison to other conventional solvent evaporation based processes including film casting and spin coating. The nanoscale stretching and ultrafast solvent removal of electrospinning lead to an enhanced apparent miscibility between the polymers, with the same blends showing micronscale phase separation when processed using film casting and spin coating. Nanoscale phase separation in electrospun blend fibers was confirmed in the dry state. Rapid, layered, macroscale phase separation of the two polymers occurred during the wetting of the fibers. This led to a biphasic drug release profile from the fibers, with a burst release from PVP-rich phases and a slower, more continuous release from HPMCAS-rich phases. It was noted that the model drug, paracetamol, had more favorable partitioning into the PVP-rich phase, which is likely to be a result of greater hydrogen bonding between PVP and paracetamol. This led to higher drug contents in the PVP-rich phases than the HPMCAS-rich phases. By alternating the proportions of the PVP and HPMCAS, the drug release rate can be modulated.

Chemical-Reaction-Controlled Phase Separated Drops: Formation, Size Selection, and Coarsening

NASA Astrophysics Data System (ADS)

Wurtz, Jean David; Lee, Chiu Fan

2018-02-01

Phase separation under nonequilibrium conditions is exploited by biological cells to organize their cytoplasm but remains poorly understood as a physical phenomenon. Here, we study a ternary fluid model in which phase-separating molecules can be converted into soluble molecules, and vice versa, via chemical reactions. We elucidate using analytical and simulation methods how drop size, formation, and coarsening can be controlled by the chemical reaction rates, and categorize the qualitative behavior of the system into distinct regimes. Ostwald ripening arrest occurs above critical reaction rates, demonstrating that this transition belongs entirely to the nonequilibrium regime. Our model is a minimal representation of the cell cytoplasm.

Heterogeneous ice nucleation on phase-separated organic-sulfate particles: effect of liquid vs. glassy coatings

NASA Astrophysics Data System (ADS)

Schill, G. P.; Tolbert, M. A.

2013-05-01

Atmospheric ice nucleation on aerosol particles relevant to cirrus clouds remains one of the least understood processes in the atmosphere. Upper tropospheric aerosols as well as sub-visible cirrus residues are known to be enhanced in both sulfates and organics. The hygroscopic phase transitions of organic-sulfate particles can have an impact on both the cirrus cloud formation mechanism and resulting cloud microphysical properties. In addition to deliquescence and efflorescence, organic-sulfate particles are known to undergo another phase transition known as liquid-liquid phase separation. The ice nucleation properties of particles that have undergone liquid-liquid phase separation are unknown. Here, Raman microscopy coupled with an environmental cell was used to study the low temperature deliquescence, efflorescence, and liquid-liquid phase separation behavior of 2 : 1 mixtures of organic polyols (1,2,6-hexanetriol and 1 : 1 1,2,6-hexanetriol + 2,2,6,6-tetrakis(hydroxymethyl)cyclohexanol) and ammonium sulfate from 240-265 K. Further, the ice nucleation efficiency of these organic-sulfate systems after liquid-liquid phase separation and efflorescence was investigated from 210-235 K. Raman mapping and volume-geometry analysis indicate that these particles contain solid ammonium sulfate cores fully engulfed in organic shells. For the ice nucleation experiments, we find that if the organic coatings are liquid, water vapor diffuses through the shell and ice nucleates on the ammonium sulfate core. In this case, the coatings minimally affect the ice nucleation efficiency of ammonium sulfate. In contrast, if the coatings become semi-solid or glassy, ice instead nucleates on the organic shell. Consistent with recent findings that glasses can be efficient ice nuclei, the phase-separated particles are nearly as efficient at ice nucleation as pure crystalline ammonium sulfate.

Heterogeneous ice nucleation on phase-separated organic-sulfate particles: effect of liquid vs. glassy coatings

NASA Astrophysics Data System (ADS)

Schill, G. P.; Tolbert, M. A.

2012-12-01

Atmospheric ice nucleation on aerosol particles relevant to cirrus clouds remains one of the least understood processes in the atmosphere. Upper tropospheric aerosols as well as sub-visible cirrus residues are known to be enhanced in both sulfates and organics. The hygroscopic phase transitions of organic-sulfate particles can have an impact on both the cirrus cloud formation mechanism and resulting cloud microphysical properties. In addition to deliquescence and efflorescence, organic-sulfate particles are known to undergo another phase transition known as liquid-liquid phase separation. The ice nucleation properties of particles that have undergone liquid-liquid phase separation are unknown. Here, Raman microscopy coupled with an environmental cell was used to study the low temperature deliquescence, efflorescence, and liquid-liquid phase separation behavior of 2:1 mixtures of organic polyols (1,2,6-hexanetriol, and 1:1 1,2,6-hexanetriol +2,2,6,6-tetrakis(hydroxymethyl)cycohexanol) and ammonium sulfate from 240-265 K. Further, the ice nucleation efficiency of these organic-sulfate systems after liquid-liquid phase separation and efflorescence was investigated from 210-235 K. Raman mapping and volume-geometry analysis indicates that these particles contain solid ammonium sulfate cores fully engulfed in organic shells. For the ice nucleation experiments, we find that if the organic coatings are liquid, water vapor diffuses through the shell and ice nucleates on the ammonium sulfate core. In this case, the coatings minimally affect the ice nucleation efficiency of ammonium sulfate. In contrast, if the coatings become semi-solid or glassy, ice instead nucleates on the organic shell. Consistent with recent findings that glasses can be efficient ice nuclei, the phase separated particles are nearly as efficient at ice nucleation as pure crystalline ammonium sulfate.

Stability and Oil Migration of Oil-in-Water Emulsions Emulsified by Phase-Separating Biopolymer Mixtures.

PubMed

Yang, Nan; Mao, Peng; Lv, Ruihe; Zhang, Ke; Fang, Yapeng; Nishinari, Katsuyoshi; Phillips, Glyn O

2016-08-01

Oil-in-water (O/W) emulsions with varying concentration of oil phase, medium-chain triglyceride (MCT), were prepared using phase-separating gum arabic (GA)/sugar beet pectin (SBP) mixture as an emulsifier. Stability of the emulsions including emulsion phase separation, droplet size change, and oil migration were investigated by means of visual observation, droplet size analysis, oil partition analysis, backscattering of light, and interfacial tension measurement. It was found that in the emulsions prepared with 4.0% GA/1.0% SBP, when the concentration of MCT was greater than 2.0%, emulsion phase separation was not observed and the emulsions were stable with droplet size unchanged during storage. This result proves the emulsification ability of phase-separating biopolymer mixtures and their potential usage as emulsifiers to prepare O/W emulsion. However, when the concentration of MCT was equal or less than 2.0%, emulsion phase separation occurred after preparation resulting in an upper SBP-rich phase and a lower GA-rich phase. The droplet size increased in the upper phase whereas decreased slightly in the lower phase with time, compared to the freshly prepared emulsions. During storage, the oil droplets exhibited a complex migration process: first moving to the SBP-rich phase, then to the GA-rich phase and finally gathering at the interface between the two phases. The mechanisms of the emulsion stability and oil migration in the phase-separated emulsions were discussed. © 2016 Institute of Food Technologists®

Advances in covalent organic frameworks in separation science.

PubMed

Qian, Hai-Long; Yang, Cheng-Xiong; Wang, Wen-Long; Yang, Cheng; Yan, Xiu-Ping

2018-03-23

Covalent organic frameworks (COFs) are a new class of multifunctional crystalline organic polymer constructed with organic monomers via robust covalent bonds. The unique properties such as convenient modification, low densities, large specific surface areas, good stability and permanent porosity make COFs great potential in separation science. This review shows the state-of-the art for the application of COFs and their composites in analytical separation science. COFs and their composites have been explored as promising sorbents for solid phase extraction, potential coatings for solid phase microextraction, and novel stationary phases for gas chromatography, high-performance liquid chromatography and capillary electrochromatography. The prospects of COFs for separation science are also presented, which can offer an outlook and reference for further study on the applications of COFs. Copyright © 2018 Elsevier B.V. All rights reserved.

Development and characterization of polyethersulfone/TiO2 mixed matrix membranes for CO2/CH4 separation

NASA Astrophysics Data System (ADS)

Galaleldin, S.; Mannan, H. A.; Mukhtar, H.

2017-12-01

In this study, mixed matrix membranes comprised of polyethersulfone as the bulk polymer phase and titanium dioxide (TiO2) nanoparticles as the inorganic discontinuous phase were prepared for CO2/CH4 separation. Membranes were synthesized at filler loading of 0, 5, 10 and 15 wt % via dry phase inversion method. Morphology, chemical bonding and thermal characteristics of membranes were scrutinized utilizing different techniques, namely: Field Emission Scanning Electron Microscopy (FESEM), Fourier Transform InfraRed (FTIR) spectra and Thermogravimetric analysis (TGA) respectively. Membranes gas separation performance was evaluated for CO2 and CH4 gases at 4 bar feed pressure. The highest separation performance was achieved by mixed matrix membrane (MMM) at 5 % loading of TiO2.

Movie of phase separation during physics of colloids in space experiment

NASA Technical Reports Server (NTRS)

2002-01-01

Still photographs taken over 16 hours on Nov. 13, 2001, on the International Space Station have been condensed into a few seconds to show the de-mixing -- or phase separation -- process studied by the Experiment on Physics of Colloids in Space. Commanded from the ground, dozens of similar tests have been conducted since the experiment arrived on ISS in 2000. The sample is a mix of polymethylmethacrylate (PMMA or acrylic) colloids, polystyrene polymers and solvents. The circular area in the video is 2 cm (0.8 in.) in diameter. The phase separation process occurs spontaneously after the sample is mechanically mixed. The evolving lighter regions are rich in colloid and have the structure of a liquid. The dark regions are poor in colloids and have the structure of a gas. This behavior carnot be observed on Earth because gravity causes the particles to fall out of solution faster than the phase separation can occur. While similar to a gas-liquid phase transition, the growth rate observed in this test is different from any atomic gas-liquid or liquid-liquid phase transition ever measured experimentally. Ultimately, the sample separates into colloid-poor and colloid-rich areas, just as oil and vinegar separate. The fundamental science of de-mixing in this colloid-polymer sample is the same found in the annealing of metal alloys and plastic polymer blends. Improving the understanding of this process may lead to improving processing of these materials on Earth.

Phase separation during the Experiment on Physics of Colloids in Space

NASA Technical Reports Server (NTRS)

2003-01-01

Still photographs taken over 16 hours on Nov. 13, 2001, on the International Space Station have been condensed into a few seconds to show the de-mixing -- or phase separation -- process studied by the Experiment on Physics of Colloids in Space. Commanded from the ground, dozens of similar tests have been conducted since the experiment arrived on ISS in 2000. The sample is a mix of polymethylmethacrylate (PMMA or acrylic) colloids, polystyrene polymers and solvents. The circular area is 2 cm (0.8 in.) in diameter. The phase separation process occurs spontaneously after the sample is mechanically mixed. The evolving lighter regions are rich in colloid and have the structure of a liquid. The dark regions are poor in colloids and have the structure of a gas. This behavior carnot be observed on Earth because gravity causes the particles to fall out of solution faster than the phase separation can occur. While similar to a gas-liquid phase transition, the growth rate observed in this test is different from any atomic gas-liquid or liquid-liquid phase transition ever measured experimentally. Ultimately, the sample separates into colloid-poor and colloid-rich areas, just as oil and vinegar separate. The fundamental science of de-mixing in this colloid-polymer sample is the same found in the annealing of metal alloys and plastic polymer blends. Improving the understanding of this process may lead to improving processing of these materials on Earth.

Fluid Phase Separation (FPS) experiment for flight on a space shuttle Get Away Special (GAS) canister

NASA Technical Reports Server (NTRS)

Peters, Bruce; Wingo, Dennis; Bower, Mark; Amborski, Robert; Blount, Laura; Daniel, Alan; Hagood, Bob; Handley, James; Hediger, Donald; Jimmerson, Lisa

1990-01-01

The separation of fluid phases in microgravity environments is of importance to environmental control and life support systems (ECLSS) and materials processing in space. A successful fluid phase separation experiment will demonstrate a proof of concept for the separation technique and add to the knowledge base of material behavior. The phase separation experiment will contain a premixed fluid which will be exposed to a microgravity environment. After the phase separation of the compound has occurred, small samples of each of the species will be taken for analysis on the Earth. By correlating the time of separation and the temperature history of the fluid, it will be possible to characterize the process. The experiment has been integrated into space available on a manifested Get Away Special (GAS) experiment, CONCAP 2, part of the Consortium for Materials Complex Autonomous Payload (CAP) Program, scheduled for STS-42. The design and the production of a fluid phase separation experiment for rapid implementation at low cost is presented.

Magnetic filtration of phase separating ferrofluids: From basic concepts to microfluidic device

NASA Astrophysics Data System (ADS)

Kuzhir, P.; Magnet, C.; Ezzaier, H.; Zubarev, A.; Bossis, G.

2017-06-01

In this work, we briefly review magnetic separation of ferrofluids composed of large magnetic particles (60 nm of the average size) possessing an induced dipole moment. Such ferrofluids exhibit field-induced phase separation at relatively low particle concentrations (∼0.8 vol%) and magnetic fields (∼10 kA/m). Particle aggregates appearing during the phase separation are extracted from the suspending fluid by magnetic field gradients much easier than individual nanoparticles in the absence of phase separation. Nanoparticle capture by a single magnetized microbead and by multi-collector systems (packed bed of spheres and micro-pillar array) has been studied both experimentally and theoretically. Under flow and magnetic fields, the particle capture efficiency Λ decreases with an increasing Mason number for all considered geometries. This decrease may become stronger for aggregated magnetic particles (Λ ∝Ma-1.7) than for individual ones (Λ ∝Ma-1) if the shear fields are strong enough to provoke aggregate rupture. These results can be useful for development of new magneto-microfluidic immunoassays based on magnetic nanoparticles offering a much better sensitivity as compared to presently used magnetic microbeads.

Nano-phase separation and structural ordering in silica-rich mixed network former glasses.

PubMed

Liu, Hao; Youngman, Randall E; Kapoor, Saurabh; Jensen, Lars R; Smedskjaer, Morten M; Yue, Yuanzheng

2018-06-13

We investigate the structure, phase separation, glass transition, and crystallization in a mixed network former glass series, i.e., B2O3-Al2O3-SiO2-P2O5 glasses with varying SiO2/B2O3 molar ratio. All the studied glasses exhibit two separate glassy phases: droplet phase (G1) with the size of 50-100 nm and matrix phase (G2), corresponding to a lower calorimetric glass transition temperature (Tg1) and a higher one (Tg2), respectively. Both Tg values decrease linearly with the substitution of B2O3 for SiO2, but the magnitude of the decrease is larger for Tg1. Based on nuclear magnetic resonance and Raman spectroscopy results, we infer that the G1 phase is rich in boroxol rings, while the G2 phase mainly involves the B-O-Si network. Both phases contain BPO4- and AlPO4-like units. Ordered domains occur in G2 upon isothermal and dynamic heating, driven by the structural heterogeneity in the as-prepared glasses. The structural ordering lowers the activation energy of crystal growth, thus promoting partial crystallization of G2. These findings are useful for understanding glass formation and phase separation in mixed network former oxide systems, and for tailoring their properties.

Liquid-Liquid Phase Separation in a Dual Variable Domain Immunoglobulin Protein Solution: Effect of Formulation Factors and Protein-Protein Interactions.

PubMed

Raut, Ashlesha S; Kalonia, Devendra S

2015-09-08

Dual variable domain immunoglobulin proteins (DVD-Ig proteins) are large molecules (MW ∼ 200 kDa) with increased asymmetry because of their extended Y-like shape, which results in increased formulation challenges. Liquid-liquid phase separation (LLPS) of protein solutions into protein-rich and protein-poor phases reduces solution stability at intermediate concentrations and lower temperatures, and is a serious concern in formulation development as therapeutic proteins are generally stored at refrigerated conditions. In the current work, LLPS was studied for a DVD-Ig protein molecule as a function of solution conditions by measuring solution opalescence. LLPS of the protein was confirmed by equilibrium studies and by visually observing under microscope. The protein does not undergo any structural change after phase separation. Protein-protein interactions were measured by light scattering (kD) and Tcloud (temperature that marks the onset of phase separation). There is a good agreement between kD measured in dilute solution with Tcloud measured in the critical concentration range. Results indicate that the increased complexity of the molecule (with respect to size, shape, and charge distribution on the molecule) increases contribution of specific and nonspecific interactions in solution, which are affected by formulation factors, resulting in LLPS for DVD-Ig protein.

Investigating the effect of V{sub 2}O{sub 5} addition on sodium barium borosilicate glasses

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

Halder, Rumu, E-mail: rumuhalder24feb@gmail.com; Sengupta, Pranesh; Dey, G. K.

2016-05-23

V{sub 2}O{sub 5} doped sodium barium borosilicate glasses were characterized by photoluminescence spectroscopy and electron probe microanalyzer (EPMA). The glass remains homogeneous for lower concentration of V{sub 2}O{sub 5} but a phase separation is observed when V{sub 2}O{sub 5} doping is increased beyond 5 mol%. Detailed microanalysis reveals that the phase separated glass consists of a phase containing V, Ba and Si and a separate Si rich phase within the glass matrix. The luminescence study demonstrated that at low concentration the vanadium mainly interacts with the structural units of B/Si while at higher concentrations, V-O-V/ V-O{sup −} Na{sup +}/Ba{sup 2+} linkagesmore » are formed.« less

New polymers for low-gravity purification of cells by phase partitioning

NASA Technical Reports Server (NTRS)

Harris, J. M.

1983-01-01

A potentially powerful technique for separating different biological cell types is based on the partitioning of these cells between the immiscible aqueous phases formed by solution of certain polymers in water. This process is gravity-limited because cells sediment rather than associate with the phase most favored on the basis of cell-phase interactions. In the present contract we have been involved in the synthesis of new polymers both to aid in understanding the partitioning process and to improve the quality of separations. The prime driving force behind the design of these polymers is to produce materials which will aid in space experiments to separate important cell types and to study the partitioning process in the absence of gravity (i.e., in an equilibrium state).

Cell Partition in Two Polymer Aqueous Phases

NASA Technical Reports Server (NTRS)

Harris, J. M.

1985-01-01

Partition of biological cells in two phase aqueous polymer systems is recognized as a powerful separation technique which is limited by gravity. The synthesis of new, selective polymer ligand conjugates to be used in affinity partition separations is of interest. The two most commonly used polymers in two phase partitioning are dextran and polyethylene glycol. A thorough review of the chemistry of these polymers was begun, particularly in the area of protein attachment. Preliminary studies indicate the importance in affinity partitioning of minimizing gravity induced randomizing forces in the phase separation process. The PEG-protein conjugates that were prepared appear to be ideally suited for achieving high quality purifications in a microgravity environment. An interesting spin-off of this synthetic work was the observation of catalytic activity for certain of our polymer derivatives.

Spectro-microscopic Characterization of Physical Properties and Phase Separations in Individual Atmospheric Particles

NASA Astrophysics Data System (ADS)

OBrien, R. E.; Wang, B.; Neu, A.; Kelly, S. T.; Lundt, N.; Epstein, S. A.; MacMillan, A.; You, Y.; Laskin, A.; Nizkorodov, S.; Bertram, A. K.; Moffet, R.; Gilles, M.

2013-12-01

The phase state and liquid-liquid phase separations of ambient and laboratory generated aerosol particles were investigated using (1) scanning transmission x-ray microscopy/near-edge x-ray absorption fine structure spectroscopy (STXM/NEXAFS) coupled to a relative humidity (RH) controlled in-situ chamber and (2) environmental scanning electron microscopy (ESEM). The phase states of the particles were determined from measurements of their size and optical density. A comparison is made between the observed phase states of ambient samples and of laboratory generated aerosols to determine how well laboratory samples represent the phase of ambient samples. In addition, liquid-liquid phase separations in laboratory generated particles were investigated. Preliminary results showing that liquid-liquid phase separations occur at RH's between the deliquescence and efflorescence points and that the organic phase surrounds the inorganic phase will be presented. The STXM/NEXAFS technique provides insight into the degree of mixing at the deliquescence point and the degree of phase separation for particles of atmospherically relevant sizes.

Green chromatography separation of analytes of greatly differing properties using a polyethylene glycol stationary phase and a low-toxic water-based mobile phase.

PubMed

Šatínský, Dalibor; Brabcová, Ivana; Maroušková, Alena; Chocholouš, Petr; Solich, Petr

2013-07-01

A simple, rapid, and environmentally friendly HPLC method was developed and validated for the separation of four compounds (4-aminophenol, caffeine, paracetamol, and propyphenazone) with different chemical properties. A "green" mobile phase, employing water as the major eluent, was proposed and applied to the separation of analytes with different polarity on polyethylene glycol (PEG) stationary phase. The chromatography separation of all compounds and internal standard benzoic acid was performed using isocratic elution with a low-toxicity mobile phase consisting of 0.04% (v/v) triethylamine and water. HPLC separation was carried out using a PEG reversed-phase stationary phase Supelco Discovery HS PEG column (15 × 4 mm; particle size 3 μm) at a temperature of 30 °C and flow rate at 1.0 mL min(-1). The UV detector was set at 210 nm. In this study, a PEG stationary phase was shown to be suitable for the efficient isocratic separation of compounds that differ widely in hydrophobicity and acid-base properties, particularly 4-aminophenol (log P, 0.30), caffeine (log P, -0.25), and propyphenazone (log P, 2.27). A polar PEG stationary phase provided specific selectivity which allowed traditional chromatographic problems related to the separation of analytes with different polarities to be solved. The retention properties of the group of structurally similar substances (aromatic amines, phenolic compounds, and xanthine derivatives) were tested with different mobile phases. The proposed green chromatography method was successfully applied to the analysis of active substances and one degradation impurity (4-aminophenol) in commercial preparation. Under the optimum chromatographic conditions, standard calibration was carried out with good linearity correlation coefficients for all compounds in the range (0.99914-0.99997, n = 6) between the peak areas and concentration of compounds. Recovery of the sample preparation was in the range 100 ± 5% for all compounds. The intraday method precision was determined as RSD, and the values were lower than 1.00%.

Incorporation of ionic liquid into porous polymer monoliths to enhance the separation of small molecules in reversed-phase high-performance liquid chromatography.

PubMed

Wang, Jiafei; Bai, Ligai; Wei, Zhen; Qin, Junxiao; Ma, Yamin; Liu, Haiyan

2015-06-01

An ionic liquid was incorporated into the porous polymer monoliths to afford stationary phases with enhanced chromatographic performance for small molecules in reversed-phase high-performance liquid chromatography. The effect of the ionic liquid in the polymerization mixture on the performance of the monoliths was studied in detail. While monoliths without ionic liquid exhibited poor resolution and low efficiency, the addition of ionic liquid to the polymerization mixture provides highly increased resolution and high efficiency. The chromatographic performances of the monoliths were demonstrated by the separations of various small molecules including aromatic hydrocarbons, isomers, and homologues using a binary polar mobile phase. The present column efficiency reached 27 000 plates/m, which showed that the ionic liquid monoliths are alternative stationary phases in the separation of small molecules by high-performance liquid chromatography. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

High-performance liquid chromatographic separations of stereoisomers of chiral basic agrochemicals with polysaccharide-based chiral columns and polar organic mobile phases.

PubMed

Matarashvili, Iza; Shvangiradze, Iamze; Chankvetadze, Lali; Sidamonidze, Shota; Takaishvili, Nino; Farkas, Tivadar; Chankvetadze, Bezhan

2015-12-01

The separation of the stereoisomers of 23 chiral basic agrochemicals was studied on six different polysaccharide-based chiral columns in high-performance liquid chromatography with various polar organic mobile phases. Along with the successful separation of analyte stereoisomers, emphasis was placed on the effect of the chiral selector and mobile phase composition on the elution order of stereoisomers. The interesting phenomenon of reversal of enantiomer/stereoisomer elution order function of the polysaccharide backbone (cellulose or amylose), type of derivative (carbamate or benzoate), nature, and position of the substituent(s) in the phenylcarbamate moiety (methyl or chloro) and the nature of the mobile phase was observed. For several of the analytes containing two chiral centers all four stereoisomers were resolved with at least one chiral selector/mobile phase combination. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Surfactant-based critical phenomena in microgravity

NASA Technical Reports Server (NTRS)

Kaler, Eric W.; Paulaitis, Michael E.

1994-01-01

The objective of this research project is to characterize by experiment and theoretically both the kinetics of phase separation and the metastable structures produced during phase separation in a microgravity environment. The particular systems we are currently studying are mixtures of water, nonionic surfactants, and compressible supercritical fluids at temperatures and pressures where the coexisting liquid phases have equal densities (isopycnic phases). In this report, we describe experiments to locate equilibrium isopycnic phases and to determine the 'local' phase behavior and critical phenomena at nearby conditions of temperature, pressure, and composition. In addition, we report the results of preliminary small angle neutron scattering (SANS) experiments to characterize microstructures that exist in these mixtures at different fluid densities.

Separation mechanism of chiral impurities, ephedrine and pseudoephedrine, found in amphetamine-type substances using achiral modifiers in the gas phase.

PubMed

Holness, Howard K; Jamal, Adeel; Mebel, Alexander; Almirall, José R

2012-11-01

A new mechanism is proposed that describes the gas-phase separation of chiral molecules found in amphetamine-type substances (ATS) by the use of high-resolution ion mobility spectrometry (IMS). Straight-chain achiral alcohols of increasing carbon chain length, from methanol to n-octanol, are used as drift gas modifiers in IMS to highlight the mechanism proposed for gas-phase separations of these chiral molecules. The results suggest the possibility of using these achiral modifiers to separate the chiral molecules (R,S) and (S,R)-ephedrine and (S,S) and (R,R)-pseudoephedrine which contain an internal hydroxyl group at the first chiral center and an amino group at the other chiral center. Ionization was achieved with an electrospray source, the ions were introduced into an IMS with a resolving power of 80, and the resulting ion clusters were characterized with a coupled quadrupole mass spectrometer detector. A complementary computational study conducted at the density functional B3LYP/6-31g level of theory for the electronic structure of the analyte-modifier clusters was also performed, and showed either "bridged" or "independent" binding. The combined experimental and simulation data support the proposed mechanism for gas-phase chiral separations using achiral modifiers in the gas phase, thus enhancing the potential to conduct fast chiral separations with relative ease and efficiency.

Monolithic poly[(trimethylsilyl-4-methylstyrene)-co- bis(4-vinylbenzyl)dimethylsilane] stationary phases for the fast separation of proteins and oligonucleotides.

PubMed

Jakschitz, Thomas A E; Huck, Christian W; Lubbad, Said; Bonn, Günther K

2007-04-13

In this paper the synthesis, optimisation and application of a silane based monolithic copolymer for the rapid separation of proteins and oligonucleotides is described. The monolith was prepared by thermal initiated in situ copolymerisation of trimethylsilyl-4-methylstyrene (TMSiMS) and bis(4-vinylbenzyl)dimethylsilane (BVBDMSi) in a silanised 200 microm I.D. fused silica column. Different ratios of monomer and crosslinker, as well as different ratios of micro- (toluene) and macro-porogen (2-propanol) were used for optimising the physical properties of the stationary phase regarding separation efficiency. The prepared monolithic stationary phases were characterised by measurement of permeability with different solvents, determination of pore size distribution by mercury intrusion porosimetry (MIP). Morphology was studied by scanning electron microscopy (SEM). Applying optimised conditions, a mixture comprised of five standard proteins ribunuclease A, cytochrome c, alpha-lactalbumine, myoglobine and ovalbumine was separated within 1 min by ion-pair reversed-phase liquid chromatography (IP-RPLC) obtaining half-height peak widths between 1.8 and 2.4 s. Baseline separation of oligonucleotides d(pT)(12-18) was achieved within 1.8 min obtaining half-height peak widths between 3.6 and 5.4 s. The results demonstrate the high potential of this stationary phase for fast separation of high-molecular weight biomolecules such as oligonucleotides and proteins.

Physics of Colloids in Space (PCS): Microgravity Experiment Completed Operations on the International Space Station

NASA Technical Reports Server (NTRS)

Doherty, Michael P.; Sankaran, Subramanian

2003-01-01

Immediately after mixing, the two-phase-like colloid-polymer critical point sample begins to phase separate, or de-mix, into two phases-one that resembles a gas and one that resembles a liquid, except that the particles are colloids and not atoms. The colloid-poor black regions (colloidal gas) grow bigger, and the colloid-rich white regions (colloidal liquid) become whiter as the domains further coarsen. Finally, complete phase separation is achieved, that is, just one region of each colloid-rich (white) and colloid-poor (black) phase. This process was studied over four decades of length scale, from 1 micrometer to 1 centimeter.

Microstructure Evolution and Related Magnetic Properties of Cu-Zr-Al-Gd Phase-Separating Metallic Glasses

NASA Astrophysics Data System (ADS)

Kim, Sang Jun; Kim, Jinwoo; Park, Eun Soo

2018-04-01

We carefully investigated the correlation between microstructures and magnetic properties of Cu-Zr-Al-Gd phase-separating metallic glasses (PSMGs). The saturation magnetizations of the PSMGs were determined by total Gd contents of the alloys, while their coercivity exhibits a large deviation by the occurrence of phase separation due to the boundary pinning effect of hierarchically separated amorphous phases. Especially, the PSMGs containing Gd-rich amorphous nanoparticles show the highest coercivity which can be attributed to the size effect of the ferromagnetic amorphous phase. Furthermore, the selective crystallization of ferromagnetic amorphous phases can affect the magnetization behavior of the PSMGs. Our results could provide a novel strategy for tailoring unique soft magnetic properties of metallic glasses by introducing hierarchically separated amorphous phases and controlling their crystallinity.

Microstructure Evolution and Related Magnetic Properties of Cu-Zr-Al-Gd Phase-Separating Metallic Glasses

NASA Astrophysics Data System (ADS)

Kim, Sang Jun; Kim, Jinwoo; Park, Eun Soo

2018-06-01

We carefully investigated the correlation between microstructures and magnetic properties of Cu-Zr-Al-Gd phase-separating metallic glasses (PSMGs). The saturation magnetizations of the PSMGs were determined by total Gd contents of the alloys, while their coercivity exhibits a large deviation by the occurrence of phase separation due to the boundary pinning effect of hierarchically separated amorphous phases. Especially, the PSMGs containing Gd-rich amorphous nanoparticles show the highest coercivity which can be attributed to the size effect of the ferromagnetic amorphous phase. Furthermore, the selective crystallization of ferromagnetic amorphous phases can affect the magnetization behavior of the PSMGs. Our results could provide a novel strategy for tailoring unique soft magnetic properties of metallic glasses by introducing hierarchically separated amorphous phases and controlling their crystallinity.

Pi-Pi contacts are an overlooked protein feature relevant to phase separation

PubMed Central

Vernon, Robert McCoy; Chong, Paul Andrew; Tsang, Brian; Kim, Tae Hun; Bah, Alaji; Farber, Patrick; Lin, Hong

2018-01-01

Protein phase separation is implicated in formation of membraneless organelles, signaling puncta and the nuclear pore. Multivalent interactions of modular binding domains and their target motifs can drive phase separation. However, forces promoting the more common phase separation of intrinsically disordered regions are less understood, with suggested roles for multivalent cation-pi, pi-pi, and charge interactions and the hydrophobic effect. Known phase-separating proteins are enriched in pi-orbital containing residues and thus we analyzed pi-interactions in folded proteins. We found that pi-pi interactions involving non-aromatic groups are widespread, underestimated by force-fields used in structure calculations and correlated with solvation and lack of regular secondary structure, properties associated with disordered regions. We present a phase separation predictive algorithm based on pi interaction frequency, highlighting proteins involved in biomaterials and RNA processing. PMID:29424691

Detecting phase separation of freeze-dried binary amorphous systems using pair-wise distribution function and multivariate data analysis.

PubMed

Chieng, Norman; Trnka, Hjalte; Boetker, Johan; Pikal, Michael; Rantanen, Jukka; Grohganz, Holger

2013-09-15

The purpose of this study is to investigate the use of multivariate data analysis for powder X-ray diffraction-pair-wise distribution function (PXRD-PDF) data to detect phase separation in freeze-dried binary amorphous systems. Polymer-polymer and polymer-sugar binary systems at various ratios were freeze-dried. All samples were analyzed by PXRD, transformed to PDF and analyzed by principal component analysis (PCA). These results were validated by differential scanning calorimetry (DSC) through characterization of glass transition of the maximally freeze-concentrate solute (Tg'). Analysis of PXRD-PDF data using PCA provides a more clear 'miscible' or 'phase separated' interpretation through the distribution pattern of samples on a score plot presentation compared to residual plot method. In a phase separated system, samples were found to be evenly distributed around the theoretical PDF profile. For systems that were miscible, a clear deviation of samples away from the theoretical PDF profile was observed. Moreover, PCA analysis allows simultaneous analysis of replicate samples. Comparatively, the phase behavior analysis from PXRD-PDF-PCA method was in agreement with the DSC results. Overall, the combined PXRD-PDF-PCA approach improves the clarity of the PXRD-PDF results and can be used as an alternative explorative data analytical tool in detecting phase separation in freeze-dried binary amorphous systems. Copyright © 2013 Elsevier B.V. All rights reserved.

[Separation and determination of eight plant hormones by reversed-phase high performance liquid chromatography].

PubMed

Fang, N; Hou, S; Shao, X; He, Y; Zhao, G

1998-09-01

In this paper, reversed-phase high performance liquid chromatographic technique was used for the separation and determination of eight plant hormones. Methanol-water-acetic acid system was chosen as the mobile phase. The effects of different separation conditions, such as the methanol and acetic acid concentrations in mobile phase, on the retention behaviours of eight plant hormones in this system were studied. The general trends in retention behaviours could be correlated to the methanol concentration in mobile phase. The experimental results showed that the optimum separation was achieved with following gradient elution condition: 0-3 minutes, 70% (water percentage in mobile phase), 3-13 minutes, 70%-20%, 13-48 minutes, 20%. Benzene was added to be as the internal standard. Under this experimental condition, the eight plant hormones could be separated completely and detected quantitatively at 260 nm within 16 minutes. The calibration curves for the eight compounds gave linearity over a wide range. The correlation coefficients of each components were r(ZT) = 0.9971, r(GAs) = 0.9999, r(K) = 0.9997, r(BA) = 0.9995, r(IAA) = 0.9998, r(IPA) = 0.9982, r(IBA) = 0.9995 and r(NAA) = 0.9995. The method is rapid, simple and efficient. It is a suitable method for the accurate determination of gibberellic acid (GA) and alpha-naphthaleneacetic acid (alpha-NAA) in products for agricultural use.

Perspective: The Asakura Oosawa model: a colloid prototype for bulk and interfacial phase behavior.

PubMed

Binder, Kurt; Virnau, Peter; Statt, Antonia

2014-10-14

In many colloidal suspensions, the micrometer-sized particles behave like hard spheres, but when non-adsorbing polymers are added to the solution a depletion attraction (of entropic origin) is created. Since 60 years the Asakura-Oosawa model, which simply describes the polymers as ideal soft spheres, is an archetypical description for the statistical thermodynamics of such systems, accounting for many features of real colloid-polymer mixtures very well. While the fugacity of the polymers (which controls their concentration in the solution) plays a role like inverse temperature, the size ratio of polymer versus colloid radii acts as a control parameter to modify the phase diagram: when this ratio is large enough, a vapor-liquid like phase separation occurs at low enough colloid packing fractions, up to a triple point where a liquid-solid two-phase coexistence region takes over. For smaller size ratios, the critical point of the phase separation and the triple point merge, resulting in a single two-phase coexistence region between fluid and crystalline phases (of "inverted swan neck"-topology, with possibly a hidden metastable phase separation). Furthermore, liquid-crystalline ordering may be found if colloidal particles of non-spherical shape (e.g., rod like) are considered. Also interactions of the particles with solid surfaces should be tunable (e.g., walls coated by polymer brushes), and interfacial phenomena are particularly interesting experimentally, since fluctuations can be studied in the microscope on all length scales, down to the particle level. Due to its simplicity this model has become a workhorse for both analytical theory and computer simulation. Recently, generalizations addressing dynamic phenomena (phase separation, crystal nucleation, etc.) have become the focus of studies.

Perspective: The Asakura Oosawa model: A colloid prototype for bulk and interfacial phase behavior

NASA Astrophysics Data System (ADS)

Binder, Kurt; Virnau, Peter; Statt, Antonia

2014-10-01

In many colloidal suspensions, the micrometer-sized particles behave like hard spheres, but when non-adsorbing polymers are added to the solution a depletion attraction (of entropic origin) is created. Since 60 years the Asakura-Oosawa model, which simply describes the polymers as ideal soft spheres, is an archetypical description for the statistical thermodynamics of such systems, accounting for many features of real colloid-polymer mixtures very well. While the fugacity of the polymers (which controls their concentration in the solution) plays a role like inverse temperature, the size ratio of polymer versus colloid radii acts as a control parameter to modify the phase diagram: when this ratio is large enough, a vapor-liquid like phase separation occurs at low enough colloid packing fractions, up to a triple point where a liquid-solid two-phase coexistence region takes over. For smaller size ratios, the critical point of the phase separation and the triple point merge, resulting in a single two-phase coexistence region between fluid and crystalline phases (of "inverted swan neck"-topology, with possibly a hidden metastable phase separation). Furthermore, liquid-crystalline ordering may be found if colloidal particles of non-spherical shape (e.g., rod like) are considered. Also interactions of the particles with solid surfaces should be tunable (e.g., walls coated by polymer brushes), and interfacial phenomena are particularly interesting experimentally, since fluctuations can be studied in the microscope on all length scales, down to the particle level. Due to its simplicity this model has become a workhorse for both analytical theory and computer simulation. Recently, generalizations addressing dynamic phenomena (phase separation, crystal nucleation, etc.) have become the focus of studies.

Selective Separation and Determination of Heavy Metals (Cd, Pb, Cr) Speciation Forms from Hortic Antrosols

NASA Astrophysics Data System (ADS)

Bulgariu, D.; Bulgariu, L.

2009-04-01

The speciation, inter-phases distribution and biodisponibility of heavy metals in soils represent one of main problem of environmental geochemistry and agro-chemistry. This problem is very important in case of hortic antrosols (soils from glasshouses) for the elimination of agricultural products (fruits, vegetables) contamination with heavy metals. In soils from glass houses, the speciation and inter-phases distribution processes of heavy metals have a particular dynamic, different in comparison with those from non-protected soils. The predominant distribution forms of heavy metals in such soils types are: complexes with low mass organic molecules, organic-mineral complexes, complexes with inorganic ligands (hydroxide-complexes, carbonate-complexes, sulphate-complexes, etc.) and basic salts. All of these have high stabilities in conditions of soils from glass houses, and in consequence, the separation and determination of speciation forms (which is directly connected with biodisponibility of heavy metals) by usual methods id very difficult and has a high uncertain degree. In this study is presented an original method for the selective separation and differentiation of speciation forms of heavy metals from glass houses soils, which is based by the combination of solid-liquid sequential extraction (SPE) with the extraction in aqueous polymer-inorganic salt two-phase systems (ABS). The soil samples used for this study have been sampled from three different locations (glass houses from Iasi, Barlad and Bacau - Romania) where the vegetables cultivation have bee performed by three different technologies. In this way was estimated the applicability and the analytical limits of method proposed by as, in function of the chemical-mineralogical and physical-chemical characteristics of soils. As heavy metals have been studied cadmium, lead and chromium, all being known for their high toxicity. The procedure used for the selective separation and differentiation of speciation forms of heavy metals from glass houses soils has two main steps: (i) non-destructive separation of chemical-mineralogical associations and aggregates from soils samples - for this the separation method with heavy liquids (bromophorme) and isodynamic magnetic method have been used; (ii) sequential extraction of heavy metals from soil fractions separated in the first step, by using combined SPE-ABS procedure. For the preparation of combined extraction systems was used polyethylene glycol (with different molecular mass: 2000, 4000 and 8000). As phase-forming inorganic salts and as selective extracting agents we have used different usual inorganic reagents. The type and concentration of phase-forming salts have been selected in function of, both nature of extracted heavy metals and chemical-mineralogical characteristics of soil samples. The experimental parameters investigated in this study are: molecular mass of polyethylene glycol and the concentration of polymeric solutions, nature and concentration of phase-forming salts, nature and concentration of extracting agents, pH in extraction system phase, type of extracted heavy metals, type of speciation forms of heavy metals and their concentrations. All these factors can influence significantly the efficiency and the selectivity of separation process. The experimental results have indicate that the combined SPE-ABS extraction systems have better separation efficiency, in comparison with traditional SPE systems and ca realized a accurate discrimination between speciation forms of heavy metals from soils. Under these conditions, the estimation of inter-phases distribution and biodisponibility of heavy metals has a high precision. On the other hand, when the combined SPE-ABS systems are used, the concomitant extraction of the elements from the same geochemical association with studied heavy metals (inevitable phenomena in case of separation by SPE procedures) is significant diminished. This increases the separation selectivity and facilitated the more accurate determination of speciation forms concentration. By adequate selection of extraction conditions can be realized the selective separation of organic-mineral complexes, which will permit to perform detailed studies about the structure and chemical composition of these. Acknowledgments The authors would like to acknowledge the financial support from Romanian Ministry of Education and Research (Project PNCDI 2-D5 no. 51045/07).

Cell separation in immunoaffinity partition in aqueous polymer two-phase systems

NASA Technical Reports Server (NTRS)

Karr, Laurel J.; Van Alstine, James M.; Snyder, Robert S.; Shafer, Steven G.; Harris, J. Milton

1989-01-01

Two methods for immunoaffinity partitioning are described. One technique involves the covalent coupling of poly (ethylene glycol) (PEG) to immunoglobulin G antibody preparations. In the second method PEG-modified Protein A is used to complex with cells and unmodified antibody. The effects of PEG molecular weight, the degree of modification, and varying phase system composition on antibody activity and its affinity for the upper phase are studied. It is observed that both methods resulted in effective cell separation.

Influence of a three-phase separator configuration on the performance of an upflow anaerobic sludge bed reactor treating wastewater from a fruit-canning factory.

PubMed

Wongnoi, Rachbordin; Songkasiri, Warinthorn; Phalakornkule, Chantaraporn

2007-02-01

The objective of this study was to investigate the influence of a three-phase separator configuration on the performance of an upflow anaerobic sludge bed (USAB) treating wastewater from a fruit canning factory. The performances of two 30-L UASB reactors--one with a modified three-phase separator giving a spiral flow pattern and the other with a conventional configuration-were investigated in parallel. Wastewater, with a chemical oxygen demand (COD) concentration between 2000 and 7000 mg/L, was obtained from a fruit-canning factory. Based on the effluent data of the first 100 operation days, the UASB with the three-phase separator giving spiral flow patterns yielded up to 25% lower biomass washout. It also showed better efficiencies in treating wastewater--up to 60% lower effluent COD, up to 20% higher COD percent removal, and up to 29% higher biogas production. This work presents evidence of an improvement on the conventional physical design of a UASB.

Vertical phase separation of 6,13-bis(triisopropylsilylethynyl) pentacene/poly(methyl methacrylate) blends prepared by electrostatic spray deposition for organic field-effect transistors

NASA Astrophysics Data System (ADS)

Onojima, Norio; Hara, Kazuhiro; Nakamura, Ayato

2017-05-01

Blend films composed of 6,13-bis(triisopropylsilylethynyl) pentacene (TIPS pentacene) and poly(methyl methacrylate) (PMMA) were prepared by electrostatic spray deposition (ESD). ESD is considered as an intermediate process between dry and wet processes since the solvent present in small droplets can almost be evaporated before arriving at the substrate. Post-drying treatments with the time-consuming evaporation of residual solvents can be omitted. However, it is still not clear that a vertically phase-separated structure can be formed in the ESD process since the vertical phase separation of the blend films is associated with the solvent evaporation. In this study, we fabricated bottom-gate, top-contact organic field-effect transistors based on the blend films prepared by ESD and the devices exhibited transistor behavior with small hysteresis. This result demonstrates that the vertical phase separation of a blend film (upper TIPS pentacene active layer/bottom PMMA gate insulator) can occur in the facile one-step ESD process.

A review of molecular phase separation in binary self-assembled monolayers of thiols on gold surfaces

NASA Astrophysics Data System (ADS)

Ong, Quy; Nianias, Nikolaos; Stellacci, Francesco

2017-09-01

Binary self-assembled monolayers (SAMs) on gold surfaces have been known to undergo molecular phase separation to various degrees and have been subject to both experimental and theoretical studies. On gold nanoparticles in particular, binary SAMs ligand shells display intriguing morphologies. Consequently, unexpected behaviors of the nanoparticles with respect to their biological, chemical, and interfacial properties have been observed. It is critical that the phase separation of binary SAMs be understood at both molecular and macroscopic level to create, and then manipulate, the useful properties of the functionalized surfaces. We look into the current understanding of molecular phase separation of binary SAMs on gold surfaces, represented by Au(111) flat surfaces and Au nanoparticles, from both theoretical and experimental aspects. We point out shortcomings and describe several research strategies that will address them in the future. Contribution to the Focus Issue Self-assemblies of Inorganic and Organic Nanomaterials edited by Marie-Pule Pileni.

Investigations on gel forming media use in low gravity bioseparations research

NASA Technical Reports Server (NTRS)

Todd, Paul; Szlag, David C.; Plank, Lindsay D.; Delcourt, Scott G.; Kunze, M. Elaine

1989-01-01

Research on gelling media and conditions suitable for the preservation of the spatial configuration of cell suspensions and macromolecular solutions after separation in free fluid during low gravity experiments is presented. The examples studied included free electrophoresis of cells in a cylindrical column and two-phase aqueous polymer separation. Microgravity electrophoresis experiments were simulated by separating model cell types (animal or human) in a vertical density gradient containing low-conductivity buffer, 1.7-6.5 percent Ficoll, 6.8-5.0 percent sucrose, and 1 percent SeaPrep low-melting temperature agarose. Upon cooling, a gel formed in the column and cells could be captured at the forming locations. Two-phase extraction experiments were simulated using two-polymer solutions in which phase separation occurs in normal saline at temperatures compatible with cell viability and in which one or both phases form a gel upon cooling. Suitable polymers included commercial agaroses (1-2 percent), maltodextrin (5-7 percent), and gelatin (5-20 percent).

Design of C18 Organic Phases with Multiple Embedded Polar Groups for Ultraversatile Applications with Ultrahigh Selectivity.

PubMed

Mallik, Abul K; Qiu, Hongdeng; Oishi, Tomohiro; Kuwahara, Yutaka; Takafuji, Makoto; Ihara, Hirotaka

2015-07-07

For the first time, we synthesized multiple embedded polar groups (EPGs) containing linear C18 organic phases. The new materials were characterized by elemental analysis, IR spectroscopy, (1)H NMR, diffuse reflectance infrared Fourier transform (DRIFT), solid-state (13)C cross-polarization magic angle spinning (CP/MAS) NMR, suspended-state (1)H NMR, and differential scanning calorimetry (DSC). (29)Si CP/MAS NMR was carried out to investigate the degree of cross-linking of the silane and silane functionality of the modified silica. Solid-state (13)C CP/MAS NMR and suspended-state (1)H NMR spectroscopy indicated a higher alkyl chain order for the phase containing four EPGs than for the phase with three EPGs. To correlate the NMR results with temperature-dependent chromatographic studies, standard reference materials (SRM 869b and SRM 1647e), a column selectivity test mixture for liquid chromatography was employed. A single EPG containing the C18 phase was also prepared in a similar manner to be used as a reference column especially for the separation of basic and polar compounds in reversed-phase liquid chromatography (RPLC) and hydrophilic interaction liquid chromatography (HILIC), respectively. Detailed chromatographic characterization of the new phases was performed in terms of their surface coverage, hydrophobic selectivity, shape selectivity, hydrogen bonding capacity, and ion-exchange capacity at pH 2.7 and 7.6 for RPLC as well as their hydrophilicity, the selectivity for hydrophilic-hydrophobic substituents, the selectivity for the region and configurational differences in hydrophilic substituents, the evaluation of electrostatic interactions, and the evaluation of the acidic-basic nature for HILIC-mode separation. Furthermore, peak shapes for the basic analytes propranolol and amitriptyline were studied as a function of the number of EPGs on the C18 phases in the RPLC. The chromatographic performance of multiple EPGs containing C18 HILIC phases is illustrated by the separation of sulfa drugs, β-blockers, xanthines, nucleic acid bases, nucleosides, and water-soluble vitamins. Both of the phases showed the best performance for the separation of shape-constrained isomers, nonpolar, polar, and basic compounds in RPLC- and HILIC-mode separation of sulfa drugs, and other polar and basic analytes compared to the conventional alkyl phases with and without embedded polar groups and HILIC phases. Surprisingly, one phase would be able to serve the performance of three different types of phases with very high selectivity, and we named this phase the "smart phase". Versatile applications with a single column will reduce the column purchasing cost for the analyst as well as achieve high separation, which is challenging with the commercially available columns.

On the phase form of a deformation quantization with separation of variables

NASA Astrophysics Data System (ADS)

Karabegov, Alexander

2016-06-01

Given a star product with separation of variables on a pseudo-Kähler manifold, we obtain a new formal (1, 1)-form from its classifying form and call it the phase form of the star product. The cohomology class of a star product with separation of variables equals the class of its phase form. We show that the phase forms can be arbitrary and they bijectively parametrize the star products with separation of variables. We also describe the action of a change of the formal parameter on a star product with separation of variables, its formal Berezin transform, classifying form, phase form, and canonical trace density.

Structural and hydrodynamic properties of an intrinsically disordered region of a germ cell-specific protein on phase separation

PubMed Central

Brady, Jacob P.; Farber, Patrick J.; Sekhar, Ashok; Lin, Yi-Hsuan; Huang, Rui; Bah, Alaji; Chan, Hue Sun; Forman-Kay, Julie D.; Kay, Lewis E.

2017-01-01

Membrane encapsulation is frequently used by the cell to sequester biomolecules and compartmentalize their function. Cells also concentrate molecules into phase-separated protein or protein/nucleic acid “membraneless organelles” that regulate a host of biochemical processes. Here, we use solution NMR spectroscopy to study phase-separated droplets formed from the intrinsically disordered N-terminal 236 residues of the germ-granule protein Ddx4. We show that the protein within the concentrated phase of phase-separated Ddx4, Ddx4cond, diffuses as a particle of 600-nm hydrodynamic radius dissolved in water. However, NMR spectra reveal sharp resonances with chemical shifts showing Ddx4cond to be intrinsically disordered. Spin relaxation measurements indicate that the backbone amides of Ddx4cond have significant mobility, explaining why high-resolution spectra are observed, but motion is reduced compared with an equivalently concentrated nonphase-separating control. Observation of a network of interchain interactions, as established by NOE spectroscopy, shows the importance of Phe and Arg interactions in driving the phase separation of Ddx4, while the salt dependence of both low- and high-concentration regions of phase diagrams establishes an important role for electrostatic interactions. The diffusion of a series of small probes and the compact but disordered 4E binding protein 2 (4E-BP2) protein in Ddx4cond are explained by an excluded volume effect, similar to that found for globular protein solvents. No changes in structural propensities of 4E-BP2 dissolved in Ddx4cond are observed, while changes to DNA and RNA molecules have been reported, highlighting the diverse roles that proteinaceous solvents play in dictating the properties of dissolved solutes. PMID:28894006

Vapor-liquid phase separator permeability results

NASA Technical Reports Server (NTRS)

Yuan, S. W. K.; Frederking, T. H. K.

1981-01-01

Continued studies are described in the area of vapor-liquid phase separator work with emphasis on permeabilities of porous sintered plugs (stainless steel, nominal pore size 2 micrometer). The temperature dependence of the permeability has been evaluated in classical fluid using He-4 gas at atmospheric pressure and in He-2 on the basis of a modified, thermosmotic permeability of the normal fluid.

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

PubMed

Raut, Ashlesha S; Kalonia, Devendra S

2015-04-01

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

Direct NMR Monitoring of Phase Separation Behavior of Highly Supersaturated Nifedipine Solution Stabilized with Hypromellose Derivatives.

PubMed

Ueda, Keisuke; Higashi, Kenjirou; Moribe, Kunikazu

2017-07-03

We investigated the phase separation behavior and maintenance mechanism of the supersaturated state of poorly water-soluble nifedipine (NIF) in hypromellose (HPMC) derivative solutions. Highly supersaturated NIF formed NIF-rich nanodroplets through phase separation from aqueous solution containing HPMC derivative. Dissolvable NIF concentration in the bulk water phase was limited by the phase separation of NIF from the aqueous solution. HPMC derivatives stabilized the NIF-rich nanodroplets and maintained the NIF supersaturation with phase-separated NIF for several hours. The size of the NIF-rich phase was different depending on the HPMC derivatives dissolved in aqueous solution, although the droplet size had no correlation with the time for which NIF supersaturation was maintained without NIF crystallization. HPMC acetate and HPMC acetate succinate (HPMC-AS) effectively maintained the NIF supersaturation containing phase-separated NIF compared with HPMC. Furthermore, HPMC-AS stabilized NIF supersaturation more effectively in acidic conditions. Solution 1 H NMR measurements of NIF-supersaturated solution revealed that HPMC derivatives distributed into the NIF-rich phase during the phase separation of NIF from the aqueous solution. The hydrophobicity of HPMC derivative strongly affected its distribution into the NIF-rich phase. Moreover, the distribution of HPMC-AS into the NIF-rich phase was promoted at lower pH due to the lower aqueous solubility of HPMC-AS. The distribution of a large amount of HPMC derivatives into NIF-rich phase induced the strong inhibition of NIF crystallization from the NIF-rich phase. Polymer distribution into the drug-rich phase directly monitored by solution NMR technique can be a useful index for the stabilization efficiency of drug-supersaturated solution containing a drug-rich phase.

Synthetic oligonucleotide separations by mixed-mode reversed-phase/weak anion-exchange liquid chromatography.

PubMed

Zimmermann, Aleksandra; Greco, Roberto; Walker, Isabel; Horak, Jeannie; Cavazzini, Alberto; Lämmerhofer, Michael

2014-08-08

Synthetic oligonucleotides gain increasing importance in new therapeutic concepts and as probes in biological sciences. If pharmaceutical-grade purities are required, chromatographic purification using ion-pair reversed-phase chromatography is commonly carried out. However, separation selectivity for structurally closely related impurities is often insufficient, especially at high sample loads. In this study, a "mixed-mode" reversed-phase/weak anion exchanger stationary phase has been investigated as an alternative tool for chromatographic separation of synthetic oligonucleotides with minor sequence variations. The employed mixed-mode phase shows great flexibility in method development. It has been run in various gradient elution modes, viz. one, two or three parameter (mixed) gradients (altering buffer pH, buffer concentration, and organic modifier) to find optimal elution conditions and gain further insight into retention mechanisms. Compared to ion-pair reversed-phase and mere anion-exchange separation, enhanced selectivities were observed with the mixed-mode phase for 20-23 nucleotide (nt) long oligonucleotides with similar sequences. Oligonucleotides differing by 1, 2 or 3 nucleotides in length could be readily resolved and separation factors for single nucleotide replacements declined in the order Cytosine (C)/Guanine (G)>Adenine (A)/Guanine∼Guanine/Thymine (T)>Adenine/Cytosine∼Cytosine/Thymine>Adenine/Thymine. Selectivities were larger when the modification was at the 3' terminal-end, declined when it was in the middle of the sequence and was smallest when it was located at the 5' terminus. Due to the lower surface area of the 200Å pore size mixed-mode stationary phase compared to the corresponding 100Å material, lower retention times with equal selectivities under milder elution conditions were achievable. Considering high sample loading capacities of the mixed-mode anion-exchanger phase, it should have great potential for chromatographic oligonucleotide separation and purification. Copyright © 2014 Elsevier B.V. All rights reserved.

Rationalizing the light-induced phase separation of mixed halide organic-inorganic perovskites.

PubMed

Draguta, Sergiu; Sharia, Onise; Yoon, Seog Joon; Brennan, Michael C; Morozov, Yurii V; Manser, Joseph S; Kamat, Prashant V; Schneider, William F; Kuno, Masaru

2017-08-04

Mixed halide hybrid perovskites, CH 3 NH 3 Pb(I 1-x Br x ) 3 , represent good candidates for low-cost, high efficiency photovoltaic, and light-emitting devices. Their band gaps can be tuned from 1.6 to 2.3 eV, by changing the halide anion identity. Unfortunately, mixed halide perovskites undergo phase separation under illumination. This leads to iodide- and bromide-rich domains along with corresponding changes to the material's optical/electrical response. Here, using combined spectroscopic measurements and theoretical modeling, we quantitatively rationalize all microscopic processes that occur during phase separation. Our model suggests that the driving force behind phase separation is the bandgap reduction of iodide-rich phases. It additionally explains observed non-linear intensity dependencies, as well as self-limited growth of iodide-rich domains. Most importantly, our model reveals that mixed halide perovskites can be stabilized against phase separation by deliberately engineering carrier diffusion lengths and injected carrier densities.Mixed halide hybrid perovskites possess tunable band gaps, however, under illumination they undergo phase separation. Using spectroscopic measurements and theoretical modelling, Draguta and Sharia et al. quantitatively rationalize the microscopic processes that occur during phase separation.

Trivalent Lanthanide/Actinide Separation Using Aqueous-Modified TALSPEAK Chemistry

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

Travis S. Grimes; Richard D. Tillotson; Leigh R. Martin

TALSPEAK is a liquid/liquid extraction process designed to separate trivalent lanthanides (Ln3+) from minor actinides (MAs) Am3+ and Cm3+. Traditional TALSPEAK organic phase is comprised of a monoacidic dialkyl bis(2-ethylhexyl)phosphoric acid extractant (HDEHP) in diisopropyl benzene (DIPB). The aqueous phase contains a soluble aminopolycarboxylate diethylenetriamine-N,N,N’,N”,N”-pentaacetic acid (DTPA) in a concentrated (1.0-2.0 M) lactic acid (HL) buffer with the aqueous acidity typically adjusted to pH 3.0. TALSPEAK balances the selective complexation of the actinides by DTPA against the electrostatic attraction of the lanthanides by the HDEHP extractant to achieve the desired trivalent lanthanide/actinide group separation. Although TALSPEAK is considered a successfulmore » separations scheme, recent fundamental studies have highlighted complex chemical interactions occurring in the aqueous and organic phases during the extraction process. Previous attempts to model the system have shown thermodynamic models do not accurately predict the observed extraction trends in the p[H+] range 2.5-4.8. In this study, the aqueous phase is modified by replacing the lactic acid buffer with a variety of simple and longer-chain amino acid buffers. The results show successful trivalent lanthanide/actinide group separation with the aqueous-modified TALSPEAK process at pH 2. The amino acid buffer concentrations were reduced to 0.5 M (at pH 2) and separations were performed without any effect on phase transfer kinetics. Successful modeling of the aqueous-modified TALSPEAK process (p[H+] 1.6-3.1) using a simplified thermodynamic model and an internally consistent set of thermodynamic data is presented.« less

Microgravity Fluid Separation Physics: Experimental and Analytical Results

NASA Technical Reports Server (NTRS)

Shoemaker, J. Michael; Schrage, Dean S.

1997-01-01

Effective, low power, two-phase separation systems are vital for the cost-effective study and utilization of two-phase flow systems and flow physics of two-phase flows. The study of microgravity flows have the potential to reveal significant insight into the controlling mechanisms for the behavior of flows in both normal and reduced gravity environments. The microgravity environment results in a reduction in gravity induced buoyancy forces acting on the discrete phases. Thus, surface tension, viscous, and inertial forces exert an increased influence on the behavior of the flow as demonstrated by the axisymmetric flow patterns. Several space technology and operations groups have studied the flow behavior in reduced gravity since gas-liquid flows are encountered in several systems such as cabin humidity control, wastewater treatment, thermal management, and Rankine power systems.

Effect of basic and acidic additives on the separation of some basic drug enantiomers on polysaccharide-based chiral columns with acetonitrile as mobile phase.

PubMed

Gogaladze, Khatuna; Chankvetadze, Lali; Tsintsadze, Maia; Farkas, Tivadar; Chankvetadze, Bezhan

2015-03-01

The separation of enantiomers of 16 basic drugs was studied using polysaccharide-based chiral selectors and acetonitrile as mobile phase with emphasis on the role of basic and acidic additives on the separation and elution order of enantiomers. Out of the studied chiral selectors, amylose phenylcarbamate-based ones more often showed a chiral recognition ability compared to cellulose phenylcarbamate derivatives. An interesting effect was observed with formic acid as additive on enantiomer resolution and enantiomer elution order for some basic drugs. Thus, for instance, the enantioseparation of several β-blockers (atenolol, sotalol, toliprolol) improved not only by the addition of a more conventional basic additive to the mobile phase, but also by the addition of an acidic additive. Moreover, an opposite elution order of enantiomers was observed depending on the nature of the additive (basic or acidic) in the mobile phase. © 2015 Wiley Periodicals, Inc.

Recovery Of Chromium Metal (VI) Using Supported Liquid Membrane (SLM) Method, A study of Influence of NaCl and pH in Receiving Phase on Transport

NASA Astrophysics Data System (ADS)

Cholid Djunaidi, Muhammad; Lusiana, Retno A.; Rahayu, Maya D.

2017-06-01

Chromium metal(VI) is a valuable metal but in contrary has high toxicity, so the separation and recovery from waste are very important. One method that can be used for the separation and recovery of chromium (VI) is a Supported Liquid Membrane (SLM). SLM system contains of three main components: a supporting membrane, organic solvents and carrier compounds. The supported Membrane used in this research is Polytetrafluoroethylene (PTFE), organic solvent is kerosene, and the carrier compound used is aliquat 336. The supported liquid membrane is placed between two phases, namely, feed phase as the source of analyte (Cr(VI)) and the receiving phase as the result of separation. Feed phase is the electroplating waste which contains of chromium metal with pH variation about 4, 6 and 9. Whereas the receiving phase are the solution of HCl, NaOH, HCl-NaCl and NaOH-NaCl with pH variation about 1, 3, 5 and 7. The efficiency separation is determined by measurement of chromium in the feed and the receiving phase using AAS (Atomic Absorption Spectrophotometry). The experiment results show that transport of Chrom (VI) by Supported Liquid membrane (SLM) is influenced by pH solution in feed phase and receiving phase as well as NaCl in receiving phase. The highest chromium metal is transported from feed phase about 97,78%, whereas in receiving phase shows about 58,09%. The highest chromium metal transport happens on pH 6 in feed phase, pH 7 in receiving phase with the mixture of NaOH and NaCl using carrier compound aliquat 336.

A Preliminary Assessment of Phase Separator Ground-Based and Reduced-Gravity Testing for ALS Systems

NASA Technical Reports Server (NTRS)

Hall, Nancy Rabel

2006-01-01

A viewgraph presentation of phase separator ground-based and reduced-gravity testing for Advanced Life Support (ALS) systems is shown. The topics include: 1) Multiphase Flow Technology Program; 2) Types of Separators; 3) MOBI Phase Separators; 4) Experiment set-up; and 5) Preliminary comparison/results.

Architecture Study on Telemetry Coverage for Immediate Post-Separation Phase

NASA Technical Reports Server (NTRS)

Cheung, Kar-Ming; Lee, Charles; Kellogg, Kent; Stocklin, Frank; Zillig, David; Fielhauer, Karl

2008-01-01

This document is the viewgraphs that accompanies a paper that presents the preliminary results of an architecture study that provides continuous telemetry coverage for NASA missions for immediate post-separation phase. After launch when the spacecraft separated from the upper stage, the spacecraft typically executes a number of mission-critical operations prior to the deployment of solar panels and the activation of the primary communication subsystem. JPL, GSFC, and APL have similar design principle statements that require continuous coverage of mission-critical telemetry during the immediate post-separation phase. To conform to these design principles, an architecture that consists of a separate spacecraft transmitter and a robust communication network capable of tracking the spacecraft signals is needed. The main results of this study are as follows: 1) At low altitude (< 10000 km) when most post-separation critical operations are executed, Earth-based network (e.g. Deep Space Network (DSN)) can only provide limited coverage, whereas space-based network (e.g. Space Network (SN)) can provide continuous coverage. 2) Commercial-off-the-shelf SN compatible transmitters are available for small satellite applications. In this paper we present the detailed coverage analysis of Earth-based and Space-based networks. We identify the key functional and performance requirements of the architecture, and describe the proposed selection criteria of the spacecraft transmitter. We conclude the paper with a proposed forward plan.

Convergence of Artificial Protein Polymers and Intrinsically Disordered Proteins.

PubMed

Dzuricky, Michael; Roberts, Stefan; Chilkoti, Ashutosh

2018-05-01

A flurry of research in recent years has revealed the molecular origins of many membraneless organelles to be the liquid phase separation of intrinsically disordered proteins (IDPs). Consequently, protein disorder has emerged as an important driver of intracellular compartmentalization by providing specialized microenvironments chemically distinct from the surrounding medium. Though the importance of protein disorder and its relationship to intracellular phase behavior are clear, a detailed understanding of how such phase behavior can be predicted and controlled remains elusive. While research in IDPs has largely focused on the implications of structural disorder on cellular function and disease, another field, that of artificial protein polymers, has focused on the de novo design of protein polymers with controllable material properties. A subset of these polymers, specifically those derived from structural proteins such as elastin and resilin, are also disordered sequences that undergo liquid-liquid phase separation. This phase separation has been used in a variety of biomedical applications, and researchers studying these polymers have developed methods to precisely characterize and tune their phase behavior. Despite their disparate origins, both fields are complementary as they study the phase behavior of intrinsically disordered polypeptides. This Perspective hopes to stimulate collaborative efforts by highlighting the similarities between these two fields and by providing examples of how such collaboration could be mutually beneficial.

Pi-Pi contacts are an overlooked protein feature relevant to phase separation.

PubMed

Vernon, Robert McCoy; Chong, Paul Andrew; Tsang, Brian; Kim, Tae Hun; Bah, Alaji; Farber, Patrick; Lin, Hong; Forman-Kay, Julie Deborah

2018-02-09

Protein phase separation is implicated in formation of membraneless organelles, signaling puncta and the nuclear pore. Multivalent interactions of modular binding domains and their target motifs can drive phase separation. However, forces promoting the more common phase separation of intrinsically disordered regions are less understood, with suggested roles for multivalent cation-pi, pi-pi, and charge interactions and the hydrophobic effect. Known phase-separating proteins are enriched in pi-orbital containing residues and thus we analyzed pi-interactions in folded proteins. We found that pi-pi interactions involving non-aromatic groups are widespread, underestimated by force-fields used in structure calculations and correlated with solvation and lack of regular secondary structure, properties associated with disordered regions. We present a phase separation predictive algorithm based on pi interaction frequency, highlighting proteins involved in biomaterials and RNA processing. © 2018, Vernon et al.

Vertical phase separation in bulk heterojunction solar cells formed by in situ polymerization of fulleride

PubMed Central

Zhang, Lipei; Xing, Xing; Zheng, Lingling; Chen, Zhijian; Xiao, Lixin; Qu, Bo; Gong, Qihuang

2014-01-01

Vertical phase separation of the donor and the acceptor in organic bulk heterojunction solar cells is crucial to improve the exciton dissociation and charge transport efficiencies. This is because whilst the exciton diffusion length is limited, the organic film must be thick enough to absorb sufficient light. However, it is still a challenge to control the phase separation of a binary blend in a bulk heterojunction device architecture. Here we report the realization of vertical phase separation induced by in situ photo-polymerization of the acrylate-based fulleride. The power conversion efficiency of the devices with vertical phase separation increased by 20%. By optimising the device architecture, the power conversion efficiency of the single junction device reached 8.47%. We believe that in situ photo-polymerization of acrylate-based fulleride is a universal and controllable way to realise vertical phase separation in organic blends. PMID:24861168

Comparison of magnesium sulfate and sodium sulfate for removal of water from pesticide extracts of foods.

PubMed

Schenck, Frank J; Callery, Patrick; Gannett, Peter M; Daft, Jonathan R; Lehotay, Steven J

2002-01-01

Water-miscible solvents, such as acetone and acetonitrile, effectively extract both polar and nonpolar pesticide residues from nonfatty foods. The addition of sodium chloride to the resulting acetonitrile-water or acetone-water extract (salting out) results in the separation of the water from the organic solvent. However, the organic solvent layer (pesticide extract) still contains some residual water, which can adversely affect separation procedures that follow, such as solid-phase extraction and/or gas chromatography. Drying agents, such as sodium sulfate or magnesium sulfate, are used to remove the water from the organic extracts. In the present study, we used nuclear magnetic resonance spectroscopy to study the composition of the phases resulting from salting out and to compare the effectiveness of sodium sulfate and magnesium sulfate as drying agents. The study showed that considerable amounts of water remained in the organic phase after phase separation. Sodium sulfate was a relatively ineffective drying agent, removing little or no residual water from the organic solvent. Magnesium sulfate proved to be a much more effective drying agent.

Monolithic metal-organic framework MIL-53(Al)-polymethacrylate composite column for the reversed-phase capillary liquid chromatography separation of small aromatics.

PubMed

Yusuf, Kareem; Badjah-Hadj-Ahmed, Ahmed Yacine; Aqel, Ahmad; ALOthman, Zeid Abdullah

2016-03-01

A monolithic capillary column containing a composite of metal-organic framework MIL-53(Al) incorporated into hexyl methacrylate-co-ethylene dimethacrylate was prepared to enhance the separation of mixtures of small aromatic compounds by using capillary liquid chromatography. The addition of 10 mg/mL MIL-53(Al) microparticles increased the micropore content in the monolithic matrix and increased the Brunauer-Emmett-Teller surface area from 26.92 to 85.12 m(2) /g. The presence of 1,4-benzenedicarboxylate moieties within the structure of MIL-53(Al) as an organic linker greatly influenced the separation of aromatic mixtures through π-π interactions. High-resolution separation was obtained for a series of alkylbenzenes (with resolution factors in the range 0.96-1.75) in less than 8 min, with 14 710 plates/m efficiency for propylbenzene, using a binary polar mobile phase of water/acetonitrile in isocratic mode. A reversed-phase separation mechanism was indicated by the increased retention factor and resolution as the water percentage in the mobile phase increased. A stability study on the composite column showed excellent mechanical stability under various conditions. The higher resolution and faster separation observed at increased temperature indicated an exothermic separation, whereas the negative values for the free energy change of transfer indicated a spontaneous process. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Method and turbine for extracting kinetic energy from a stream of two-phase fluid

NASA Technical Reports Server (NTRS)

Elliott, D. G. (Inventor)

1979-01-01

An axial flow separator turbine is described which includes a number of nozzles for delivering streams of a two-phase fluid along linear paths. A phase separator which responsively separates the vapor and liquid is characterized by concentrically related annuli supported for rotation within the paths. The separator has endless channels for confining the liquid under the influence of centrifugal forces. A vapor turbine fan extracts kinetic energy from the liquid. Angular momentum of both the liquid phase and the vapor phase of the fluid is converted to torque.

Ionic liquid/water mixtures: from hostility to conciliation.

PubMed

Kohno, Yuki; Ohno, Hiroyuki

2012-07-21

Water was originally inimical to ionic liquids (ILs) especially in the analysis of their detailed properties. Various data on the properties of ILs indicate that there are two ways to design functions of ionic liquids. The first is to change the structure of component ions, to provide "task-specific ILs". The second is to mix ILs with other components, such as other ILs, organic solvents or water. Mixing makes it easy to control the properties of the solution. In this strategy, water is now a very important partner. Below, we summarise our recent results on the properties of IL/water mixtures. Stable phase separation is an effective method in some separation processes. Conversely, a dynamic phase change between a homogeneous mixture and separation of phases is important in many fields. Analysis of the relation between phase behaviour and the hydration state of the component ions indicates that the pattern of phase separation is governed by the hydrophilicity of the ions. Sufficiently hydrophilic ions yielded ILs that are miscible with water, and hydrophobic ions gave stable phase separation with water. ILs composed of hydrophobic but hydrated ions undergo a dynamic phase change between a homogeneous mixture and separate phases according to temperature. ILs having more than seven water molecules per ion pair undergo this phase transition. These dynamic phase changes are considered, with some examples, and application is made to the separation of water-soluble proteins.

Integrated method of thermosensitive triblock copolymer-salt aqueous two phase extraction and dialysis membrane separation for purification of lycium barbarum polysaccharide.

PubMed

Wang, Yun; Hu, Xiaowei; Han, Juan; Ni, Liang; Tang, Xu; Hu, Yutao; Chen, Tong

2016-03-01

A polymer-salt aqueous two-phase system (ATPS) consisting of thermosensitive copolymer ethylene-oxide-b-propylene-oxide-b-ethylene-oxide (EOPOEO) and NaH2PO4 was employed in deproteinization for lycium barbarum polysaccharide (LBP). The effects of salt type and concentration, EOPOEO concentration, amount of crude LBP solution and temperature were studied. In the primary extraction process, LBP was preferentially partitioned to the bottom (salt-rich) phase with high recovery ratio of 96.3%, while 94.4% of impurity protein was removed to the top (EOPOEO-rich) phase. Moreover, the majority of pigments could be discarded to top phase. After phase-separation, the LBP in the bottom phase was further purified by dialysis membrane to remove salt and other small molecular impurities. The purity of LBP was enhanced to 64%. Additionally, the FT-IR spectrum was used to identify LBP. EOPOEO was recovered by a temperature-induced separation, and reused in a new ATPS. An ideal extraction and recycle result were achieved. Copyright © 2015 Elsevier Ltd. All rights reserved.

Improving reliability of a residency interview process.

PubMed

Peeters, Michael J; Serres, Michelle L; Gundrum, Todd E

2013-10-14

To improve the reliability and discrimination of a pharmacy resident interview evaluation form, and thereby improve the reliability of the interview process. In phase 1 of the study, authors used a Many-Facet Rasch Measurement model to optimize an existing evaluation form for reliability and discrimination. In phase 2, interviewer pairs used the modified evaluation form within 4 separate interview stations. In phase 3, 8 interviewers individually-evaluated each candidate in one-on-one interviews. In phase 1, the evaluation form had a reliability of 0.98 with person separation of 6.56; reproducibly, the form separated applicants into 6 distinct groups. Using that form in phase 2 and 3, our largest variation source was candidates, while content specificity was the next largest variation source. The phase 2 g-coefficient was 0.787, while confirmatory phase 3 was 0.922. Process reliability improved with more stations despite fewer interviewers per station-impact of content specificity was greatly reduced with more interview stations. A more reliable, discriminating evaluation form was developed to evaluate candidates during resident interviews, and a process was designed that reduced the impact from content specificity.

Preparation and evaluation of diblock copolymer-grafted silica by sequential surface initiated-atom transfer radical polymerization for reverse-phase/ion-exchange mixed-mode chromatography.

PubMed

Bo, Chun Miao; Wang, Chaozhan; Wei, Yin Mao

2017-12-01

A novel approach that involved the grafting of diblock copolymer with two types of monomer onto substrate by sequential surface initiated-atom transfer radical polymerization was proposed to prepare a mixed-mode chromatographic stationary phase. The distinguishing feature of this method is that it can be applied in the preparation of various mixed-mode stationary phases. In this study, a new reverse-phase/ion-exchange stationary phase was prepared by grafting hydrophobic styrene and cationic sodium 4-styrenesulfonate by the proposed approach onto silica surface. The chromatographic properties of the prepared stationary phase were evaluated by the separation of benzene derivatives, anilines, and β-agonists, and by the effect of pH values and acetonitrile content on the retention. Compared with typical RP columns, the prepared stationary phase achieved the better resolution and higher selectivity at a shorter separation time and lower organic content. Moreover, the application of the prepared column was proved by separating widely distributed polar and charged compounds simultaneously. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A simple transferable adaptive potential to study phase separation in large-scale xMgO-(1-x)SiO2 binary glasses.

PubMed

Bidault, Xavier; Chaussedent, Stéphane; Blanc, Wilfried

2015-10-21

A simple transferable adaptive model is developed and it allows for the first time to simulate by molecular dynamics the separation of large phases in the MgO-SiO2 binary system, as experimentally observed and as predicted by the phase diagram, meaning that separated phases have various compositions. This is a real improvement over fixed-charge models, which are often limited to an interpretation involving the formation of pure clusters, or involving the modified random network model. Our adaptive model, efficient to reproduce known crystalline and glassy structures, allows us to track the formation of large amorphous Mg-rich Si-poor nanoparticles in an Mg-poor Si-rich matrix from a 0.1MgO-0.9SiO2 melt.

Competing phases, phase separation, and coexistence in the extended one-dimensional bosonic Hubbard model

DOE PAGES

Batrouni, G. G.; Rousseau, V. G.; Scalettar, R. T.; ...

2014-11-17

Here, we study the phase diagram of the one-dimensional bosonic Hubbard model with contact (U) and near neighbor (V ) interactions focusing on the gapped Haldane insulating (HI) phase which is characterized by an exotic nonlocal order parameter. The parameter regime (U, V and μ) where this phase exists and how it competes with other phases such as the supersolid (SS) phase, is incompletely understood. We use the Stochastic Green Function quantum Monte Carlo algorithm as well as the density matrix renormalization group to map out the phase diagram. The HI exists only at = 1, the SS phase existsmore » for a very wide range of parameters (including commensurate fillings) and displays power law decay in the one body Green function were our main conclusions. Additionally, we show that at fixed integer density, the system exhibits phase separation in the (U, V ) plane.« less

Polysaccharide-derived mesoporous materials (Starbon®) for sustainable separation of complex mixtures.

PubMed

Zuin, Vânia G; Budarin, Vitaliy L; De Bruyn, Mario; Shuttleworth, Peter S; Hunt, Andrew J; Pluciennik, Camille; Borisova, Aleksandra; Dodson, Jennifer; Parker, Helen L; Clark, James H

2017-09-21

The recovery and separation of high value and low volume extractives are a considerable challenge for the commercial realisation of zero-waste biorefineries. Using solid-phase extractions (SPE) based on sustainable sorbents is a promising method to enable efficient, green and selective separation of these complex extractive mixtures. Mesoporous carbonaceous solids derived from renewable polysaccharides are ideal stationary phases due to their tuneable functionality and surface structure. In this study, the structure-separation relationships of thirteen polysaccharide-derived mesoporous materials and two modified types as sorbents for ten naturally-occurring bioactive phenolic compounds were investigated. For the first time, a comprehensive statistical analysis of the key molecular and surface properties influencing the recovery of these species was carried out. The obtained results show the possibility of developing tailored materials for purification, separation or extraction, depending on the molecular composition of the analyte. The wide versatility and application span of these polysaccharide-derived mesoporous materials offer new sustainable and inexpensive alternatives to traditional silica-based stationary phases.

Chiral separations of cathinone and amphetamine-derivatives: Comparative study between capillary electrochromatography, supercritical fluid chromatography and three liquid chromatographic modes.

PubMed

Albals, Dima; Heyden, Yvan Vander; Schmid, Martin G; Chankvetadze, Bezhan; Mangelings, Debby

2016-03-20

The screening part of an earlier defined chiral separation strategy in capillary electrochromatography (CEC) was used for the separation of ten cathinone- and amphetamine derivatives. They were analyzed using 4 polysaccharide-based chiral stationary phases (CSPs), containing cellulose tris(3,5-dimethylphenylcarbamate) (ODRH), amylose tris(3,5-dimethylphenylcarbamate) (ADH), amylose tris(5-chloro-2-methylphenylcarbamate) (LA2), and cellulose tris(4-chloro-3-methylphenylcarbamate) (LC4) as chiral selectors. After applying the screening to each compound, ADH and LC4 showed the highest success rate. In a second part of the study, a comparison between CEC and other analytical techniques used for chiral separations i.e., supercritical fluid chromatography (SFC), polar organic solvent chromatography (POSC), reversed-phase (RPLC) and normal-phase liquid chromatography (NPLC), was made. For this purpose, earlier defined screening approaches for each technique were applied to separate the 10 test substances. This allowed an overall comparison of the success rates of the screening steps of the 5 techniques for these compounds. The results showed that CEC had a similar enantioselectivity rate as NPLC and RPLC, producing the highest number of separations (9 out of 10 racemates). SFC resolved 7 compounds, while POSC gave only 2 separations. On the other hand, the baseline separation success rates for NPLC and RPLC was better than for CEC. For a second comparison, the same chiral stationary phases as in the CEC screening were also tested with all techniques at their specific screening conditions, which allowed a direct comparison of the performance of CEC versus the same CSPs in the other techniques. This comparison revealed that RPLC was able to separate all tested compounds, and also produced the highest number of baseline separations on the CSP that were used in the CEC screening step. CEC and NPLC showed the same success rate: nine out of ten substances were separated. When CEC and NPLC are combined, separation of the ten compounds can be achieved. SFC and POSC resolved eight and three compounds, respectively. POSC was the least attractive option as it expressed only limited enantioselectivity toward these compounds. Copyright © 2015 Elsevier B.V. All rights reserved.

Hydrophilic interaction liquid chromatography in the speciation analysis of selenium.

PubMed

Sentkowska, Aleksandra; Pyrzynska, Krystyna

2018-02-01

The hydrophilic interaction liquid chromatography (HILIC) coupled to mass spectrometry was employed to study retention behavior of selected selenium compounds using two different HILIC stationary phases: silica and zwitterionic. Two organic solvents - acetonitrile and methanol - were compared as a component of mobile phase. Separation parameters such as a content of organic modifier, the eluent pH and inorganic buffer concentration were investigated. Based on all observations, methanol seems to be beneficial for the separation of studied compounds. The optimal HILIC separation method involved silica column and eluent composed of 85% MeOH and CH 3 COONH 4 (8 mM, pH 7) was compared to RP method in terms of time of the single run, the separation efficiency and limit of detection. Copyright © 2018 Elsevier B.V. All rights reserved.

Phase behaviour of casein micelles and barley beta-glucan polymer molecules in dietary fibre-enriched dairy systems.

PubMed

Repin, Nikolay; Scanlon, Martin G; Fulcher, R Gary

2012-07-01

Enrichment of colloidal dairy systems with dietary fibre frequently causes quality defects because of phase separation. We investigate phase separation in skimmed milk enriched with Glucagel (a commercial product made from barley that is predominantly comprised of the polysaccharide β-glucan). The driving force for phase separation was depletion flocculation of casein micelles in the presence of molecules of the polysaccharide. Depending on the volume fraction of casein micelles and the concentration of Glucagel, the stable system phase separated either as a transient gel or as a sedimented system. The rate at which phase separation progressed also depended on the volume fraction of casein micelles and the concentration of Glucagel. To confirm the role of depletion flocculation in the phase separation process, enzymatic reduction in the molecular weight of β-glucan was shown to limit the range of attraction between micelles and allow the stable phase to exist at a higher β-glucan concentration for any given volume fraction of casein micelles. These phase diagrams will be useful to dairy product manufacturers striving to improve the nutrient profile of their products while avoiding product quality impairment. Copyright © 2012 Elsevier Inc. All rights reserved.

The rheology and phase separation kinetics of mixed-matrix membrane dopes

NASA Astrophysics Data System (ADS)

Olanrewaju, Kayode Olaseni

Mixed-matrix hollow fiber membranes are being developed to offer more efficient gas separations applications than what the current technologies allow. Mixed-matrix membranes (MMMs) are membranes in which molecular sieves incorporated in a polymer matrix enhance separation of gas mixtures based on the molecular size difference and/or adsorption properties of the component gases in the molecular sieve. The major challenges encountered in the efficient development of MMMs are associated with some of the paradigm shifts involved in their processing, as compared to pure polymer membranes. For instance, mixed-matrix hollow fiber membranes are prepared by a dry-wet jet spinning method. Efficient large scale processing of hollow fibers by this method requires knowledge of two key process variables: the rheology and kinetics of phase separation of the MMM dopes. Predicting the rheological properties of MMM dopes is not trivial; the presence of particles significantly affects neat polymer membrane dopes. Therefore, the need exists to characterize and develop predictive capabilities for the rheology of MMM dopes. Furthermore, the kinetics of phase separation of polymer solutions is not well understood. In the case of MMM dopes, the kinetics of phase separation are further complicated by the presence of porous particles in a polymer solution. Thus, studies on the phase separation kinetics of polymer solutions and suspensions of zeolite particles in polymer solutions are essential. Therefore, this research thesis aims to study the rheology and phase separation kinetics of mixed-matrix membrane dopes. In our research efforts to develop predictive models for the shear rheology of suspensions of zeolite particles in polymer solutions, it was found that MFI zeolite suspensions have relative viscosities that dramatically exceed the Krieger-Dougherty predictions for hard sphere suspensions. Our investigations showed that the major origin of this discrepancy is the selective absorption of solvent molecules from the suspending polymer solution into the zeolite pores. Consequently, both the viscosity of the polymer solution and the particle contribution to the suspension viscosity are greatly increased. A predictive model for the viscosity of porous zeolite suspensions incorporating a solvent absorption parameter, alpha, into the Krieger-Dougherty model was developed. We experimentally determined the solvent absorption parameter and our results are in good agreement with the theoretical pore volume of MFI particles. In addition, fundamental studies were conducted with spherical nonporous silica suspensions to elucidate the role of colloidal and hydrodynamic forces on the rheology of mixed-matrix membrane dopes. Also in this thesis, details of a novel microfluidic device for measuring the phase separation kinetics of membrane dopes are presented. We have used this device to quantify the phase separation kinetics (PSK) of polymer solutions and MMM dopes upon contact with an array of relevant nonsolvent. For the polymer solution, we found that PSK is governed by the micro-rheological and thermodynamic properties of the polymer solution and nonsolvent. For the MMM dopes, we found that the PSK may increase with increase in particles surface area due to surface diffusion enhancement. In addition, it was found that the dispersed particles alter the thermodynamic properties of the dope based on the hydrophilicity and porosity of the particle.

Fluid Phase Separation (FPS) experiment for flight on the shuttle in a Get Away Special (GAS) canister: Design and fabrication

NASA Technical Reports Server (NTRS)

1990-01-01

The separation of fluid phases in microgravity environments is of importance to environmental control and life support systems (ECLSS) and materials processing in space. A successful fluid phase separation experiment will demonstrate a proof of concept for the separation technique and add to the knowledge base of material behavior. The phase separation experiment will contain a premixed fluid that will be exposed to a microgravity environment. After the phase separation of the compound has occurred, small samples of each of the species will be taken for analysis on Earth. By correlating the time of separation and the temperature history of the fluid, it will be possible to characterize the process. The phase separation experiment is totally self-contained, with three levels of containment on all fluids, and provides all necessary electrical power and control. The controller regulates the temperature of the fluid and controls data logging and sampling. An astronaut-activated switch will initiate the experiment and an unmaskable interrupt is provided for shutdown. The experiment has been integrated into space available on a manifested Get Away Special (GAS) experiment, CONCAP 2, part of the Consortium for Materials Complex Autonomous Payload (CAP) Program, scheduled for STS 42 in April 1991. Presented here are the design and the production of a fluid phase separation experiment for rapid implementation at low cost.

[Isolation and preparation of an imidazole alkaloid from radix radix of Aconitum pendulum Busch by semi-preparative high-speed counter-current chromatography].

PubMed

Liu, Yongling; Chen, Tao; Chen, Chen; Zou, Denglang; Li, Yulin

2014-05-01

Aconitum pendulum Busch is rich C19 diterpenoid alkaloids, but there is no report of imidazole alkaloid in Aconitum pendulum Busch. In this study, an imidazole alkaloid named 1H-imidazole-2-carboxylic acid, butyl ester (ICABE) was successfully separated from Aconitum pendulum Busch with semi-preparative high-speed counter-current chromatography (HSCCC). The partition coefficient was measured by HPLC to select the solvent systems for ICABE separation by HSCCC. The separation was performed with a two-phase solvent system composed of n-hexane-chloroform-ethanol-water (10:1 : 13:2, v/v/v/v). The upper phase was used as the stationary phase and the lower phase as the mobile phase. It was operated at a flow rate of 1.8 mL/min. The apparatus was rotated at 850 r/min, and the detection wavelength was set at 230 nm. Under the selected conditions, a high efficiency separation of HSCCC was achieved, and 7.5 mg of ICABE was obtained from 100 mg of the crude sample of Aconitum pendulum in one-step separation within 350 min. The HPLC analysis showed that the purity of the compound was over 98%. The chemical structure was confirmed by UV, 1H-NMR and 13C-NMR. The established method is simple, highly efficient and suitable for large scale separation of ICABE from radix of Aconitum pendulum Busch.

Advanced flight hardware for organic separations using aqueous two-phase partitioning

NASA Astrophysics Data System (ADS)

Deuser, Mark S.; Vellinger, John C.; Weber, John T.

1996-03-01

Separation of cells and cell components is the limiting factor in many biomedical research and pharmaceutical development processes. Aqueous Two-Phase Partitioning (ATPP) is a unique separation technique which allows purification and classification of biological materials. SHOT has employed the ATPP process in separation equipment developed for both space and ground applications. Initial equipment development and research focused on the ORganic SEParation (ORSEP) space flight experiments that were performed on suborbital rockets and the shuttle. ADvanced SEParations (ADSEP) technology was developed as the next generation of ORSEP equipment through a NASA Small Business Innovation Research (SBIR) contract. Under the SBIR contract, a marketing study was conducted, indicating a growing commercial market exists among biotechnology firms for ADSEP equipment and associated flight research and development services. SHOT is preparing to begin manufacturing and marketing laboratory versions of the ADSEP hardware for the ground-based market. In addition, through a self-financed SBIR Phase III effort, SHOT is fabricating and integrating the ADSEP flight hardware for a commercially-driven SPACEHAB 04 experiment that will be the initial step in marketing space separations services. The ADSEP ground-based and microgravity research is expected to play a vital role in developing important new biomedical and pharmaceutical products.

Evaporation and Degradation of a Sessile Droplet of VX on an Impermeable Surface

DTIC Science & Technology

2017-09-01

NOTES 14. ABSTRACT: This report highlights experimental studies into the combined physical and chemical processes that occur when a sessile droplet...resulting chemical change causes a corresponding change in the contact angle and evaporation rate of the sessile droplet on an impermeable surface...for phase separation. 15. SUBJECT TERMS Chemical degradation Phase separation Contact angle 2-(diisopropylamino)ethyl-O-ethyl

Phase separation and second-order phase transition in the phenomenological model for a Coulomb-frustrated two-dimensional system

NASA Astrophysics Data System (ADS)

Mamin, R. F.; Shaposhnikova, T. S.; Kabanov, V. V.

2018-03-01

We have considered the model of the phase transition of the second order for the Coulomb frustrated 2D charged system. The coupling of the order parameter with the charge was considered as the local temperature. We have found that in such a system, an appearance of the phase-separated state is possible. By numerical simulation, we have obtained different types ("stripes," "rings," "snakes") of phase-separated states and determined the parameter ranges for these states. Thus the system undergoes a series of phase transitions when the temperature decreases. First, the system moves from the homogeneous state with a zero order parameter to the phase-separated state with two phases in one of which the order parameter is zero and, in the other, it is nonzero (τ >0 ). Then a first-order transition occurs to another phase-separated state, in which both phases have different and nonzero values of the order parameter (for τ <0 ). Only a further decrease of temperature leads to a transition to a homogeneous ordered state.

Separating homeologs by phasing in the tetraploid wheat transcriptome.

PubMed

Krasileva, Ksenia V; Buffalo, Vince; Bailey, Paul; Pearce, Stephen; Ayling, Sarah; Tabbita, Facundo; Soria, Marcelo; Wang, Shichen; Akhunov, Eduard; Uauy, Cristobal; Dubcovsky, Jorge

2013-06-25

The high level of identity among duplicated homoeologous genomes in tetraploid pasta wheat presents substantial challenges for de novo transcriptome assembly. To solve this problem, we develop a specialized bioinformatics workflow that optimizes transcriptome assembly and separation of merged homoeologs. To evaluate our strategy, we sequence and assemble the transcriptome of one of the diploid ancestors of pasta wheat, and compare both assemblies with a benchmark set of 13,472 full-length, non-redundant bread wheat cDNAs. A total of 489 million 100 bp paired-end reads from tetraploid wheat assemble in 140,118 contigs, including 96% of the benchmark cDNAs. We used a comparative genomics approach to annotate 66,633 open reading frames. The multiple k-mer assembly strategy increases the proportion of cDNAs assembled full-length in a single contig by 22% relative to the best single k-mer size. Homoeologs are separated using a post-assembly pipeline that includes polymorphism identification, phasing of SNPs, read sorting, and re-assembly of phased reads. Using a reference set of genes, we determine that 98.7% of SNPs analyzed are correctly separated by phasing. Our study shows that de novo transcriptome assembly of tetraploid wheat benefit from multiple k-mer assembly strategies more than diploid wheat. Our results also demonstrate that phasing approaches originally designed for heterozygous diploid organisms can be used to separate the close homoeologous genomes of tetraploid wheat. The predicted tetraploid wheat proteome and gene models provide a valuable tool for the wheat research community and for those interested in comparative genomic studies.

Separating homeologs by phasing in the tetraploid wheat transcriptome

PubMed Central

2013-01-01

Background The high level of identity among duplicated homoeologous genomes in tetraploid pasta wheat presents substantial challenges for de novo transcriptome assembly. To solve this problem, we develop a specialized bioinformatics workflow that optimizes transcriptome assembly and separation of merged homoeologs. To evaluate our strategy, we sequence and assemble the transcriptome of one of the diploid ancestors of pasta wheat, and compare both assemblies with a benchmark set of 13,472 full-length, non-redundant bread wheat cDNAs. Results A total of 489 million 100 bp paired-end reads from tetraploid wheat assemble in 140,118 contigs, including 96% of the benchmark cDNAs. We used a comparative genomics approach to annotate 66,633 open reading frames. The multiple k-mer assembly strategy increases the proportion of cDNAs assembled full-length in a single contig by 22% relative to the best single k-mer size. Homoeologs are separated using a post-assembly pipeline that includes polymorphism identification, phasing of SNPs, read sorting, and re-assembly of phased reads. Using a reference set of genes, we determine that 98.7% of SNPs analyzed are correctly separated by phasing. Conclusions Our study shows that de novo transcriptome assembly of tetraploid wheat benefit from multiple k-mer assembly strategies more than diploid wheat. Our results also demonstrate that phasing approaches originally designed for heterozygous diploid organisms can be used to separate the close homoeologous genomes of tetraploid wheat. The predicted tetraploid wheat proteome and gene models provide a valuable tool for the wheat research community and for those interested in comparative genomic studies. PMID:23800085

Effect of temperature gradient on liquid-liquid phase separation in a polyolefin blend.

PubMed

Jiang, Hua; Dou, Nannan; Fan, Guoqiang; Yang, Zhaohui; Zhang, Xiaohua

2013-09-28

We have investigated experimentally the structure formation processes during phase separation via spinodal decomposition above and below the spinodal line in a binary polymer blend system exposed to in-plane stationary thermal gradients using phase contrast optical microscopy and temperature gradient hot stage. Below the spinodal line there is a coupling of concentration fluctuations and thermal gradient imposed by the temperature gradient hot stage. Also under the thermal gradient annealing phase-separated domains grow faster compared with the system under homogeneous temperature annealing on a zero-gradient or a conventional hot stage. We suggest that the in-plane thermal gradient accelerates phase separation through the enhancement in concentration fluctuations in the early and intermediate stages of spinodal decomposition. In a thermal gradient field, the strength of concentration fluctuation close to the critical point (above the spinodal line) is strong enough to induce phase separation even in one-phase regime of the phase diagram. In the presence of a temperature gradient the equilibrium phase diagrams are no longer valid, and the systems with an upper critical solution temperature can be quenched into phase separation by applying the stationary temperature gradient. The in-plane temperature gradient drives enhanced concentration fluctuations in a binary polymer blend system above and below the spinodal line.

Amide-induced phase separation of hexafluoroisopropanol-water mixtures depending on the hydrophobicity of amides.

PubMed

Takamuku, Toshiyuki; Wada, Hiroshi; Kawatoko, Chiemi; Shimomura, Takuya; Kanzaki, Ryo; Takeuchi, Munetaka

2012-06-21

Amide-induced phase separation of hexafluoro-2-propanol (HFIP)-water mixtures has been investigated to elucidate solvation properties of the mixtures by means of small-angle neutron scattering (SANS), (1)H and (13)C NMR, and molecular dynamics (MD) simulation. The amides included N-methylformamide (NMF), N-methylacetamide (NMA), and N-methylpropionamide (NMP). The phase diagrams of amide-HFIP-water ternary systems at 298 K showed that phase separation occurs in a closed-loop area of compositions as well as an N,N-dimethylformamide (DMF) system previously reported. The phase separation area becomes wider as the hydrophobicity of amides increases in the order of NMF < NMA < DMF < NMP. Thus, the evolution of HFIP clusters around amides due to the hydrophobic interaction gives rise to phase separation of the mixtures. In contrast, the disruption of HFIP clusters causes the recovery of the homogeneity of the ternary systems. The present results showed that HFIP clusters are evolved with increasing amide content to the lower phase separation concentration in the same mechanism among the four amide systems. However, the disruption of HFIP clusters in the NMP and DMF systems with further increasing amide content to the upper phase separation concentration occurs in a different way from those in the NMF and NMA systems.

Phase separations in mixtures of a liquid crystal and a nanocolloidal particle.

PubMed

Matsuyama, Akihiko

2009-11-28

We present a mean field theory to describe phase separations in mixtures of a liquid crystal and a nanocolloidal particle. By taking into account a nematic, a smectic A ordering of the liquid crystal, and a crystalline ordering of the nanoparticle, we calculate the phase diagrams on the temperature-concentration plane. We predict various phase separations, such as a smectic A-crystal phase separation and a smectic A-isotropic-crystal triple point, etc., depending on the interactions between the liquid crystal and the colloidal surface. Inside binodal curves, we find new unstable and metastable regions, which are important in the phase ordering dynamics. We also find a crystalline ordering of the nanoparticles dispersed in a smectic A phase and a nematic phase. The cooperative phenomena between liquid-crystalline ordering and crystalline ordering induce a variety of phase diagrams.

Kinetics of phase separation and coarsening in dilute surfactant pentaethylene glycol monododecyl ether solutions

NASA Astrophysics Data System (ADS)

Tanaka, S.; Kubo, Y.; Yokoyama, Y.; Toda, A.; Taguchi, K.; Kajioka, H.

2011-12-01

We investigated the phase separation phenomena in dilute surfactant pentaethylene glycol monodedecyl ether (C12E5) solutions focusing on the growth law of separated domains. The solutions confined between two glass plates were found to exhibit the phase inversion, characteristic of the viscoelastic phase separation; the majority phase (water-rich phase) nucleated as droplets and the minority phase (micelle-rich phase) formed a network temporarily, then they collapsed into an usual sea-island pattern where minority phase formed islands. We found from the real-space microscopic imaging that the dynamic scaling hypothesis did not hold throughout the coarsening process. The power law growth of the domains with the exponent close to 1/3 was observed even though the coarsening was induced mainly by hydrodynamic flow, which was explained by Darcy's law of laminar flow.

Separation of furostanol saponins by supercritical fluid chromatography.

PubMed

Yang, Jie; Zhu, Lingling; Zhao, Yang; Xu, Yongwei; Sun, Qinglong; Liu, Shuchen; Liu, Chao; Ma, Baiping

2017-10-25

Supercritical fluid chromatography (SFC) has good separation efficiency and is suitable for separating weakly polar compounds. Furostanol saponins, as an important kind of steroidal saponins, generally have two sugar chains, which are polar and hydrophilic. The hydroxyl group at the C-22 position of furostanol saponins is active and easily reacts with lower alcohols under appropriate conditions. The separation of hydrophilic furostanol saponins was tested by SFC in this study. The effects of chromatographic conditions on the separation of the mixed furostanol saponins and their hydroxyl derivatives at the C-22 position were studied. The conditions for SFC, which included different column polarity, modifier, additive, and column temperature, were tested. After optimization, the mixed 10 similar structures of furostanol saponins were separated in 22min on the Diol column at a temperature of 40°C. The mobile phase was CO 2 (mobile phase A) and methanol (containing 0.2% NH 3 ∙H 2 O and 3% H 2 O) (mobile phase B). The backpressure was maintained isobarically at 11.03MPa. SFC was found to be effective in separating the furostanol saponins that shared the same aglycone but varied in sugar chains. SFC was sensitive to the number and type of sugars. The resolution of furostanol saponin isomers was not ideal. The extract of Dioscorea zingiberensis C. H. Wright was profiled by SFC-quadrupole time-of-flight mass spectrometry. The main saponins of the extract were well separated. Therefore, SFC could be used for separating hydrophilic furostanol saponins and analyzing traditional Chinese medicines that mainly contained steroidal saponins. Copyright © 2017 Elsevier B.V. All rights reserved.

Polymer-induced phase separation and crystallization in immunoglobulin G solutions.

PubMed

Li, Jianguo; Rajagopalan, Raj; Jiang, Jianwen

2008-05-28

We study the effects of the size of polymer additives and ionic strength on the phase behavior of a nonglobular protein-immunoglobulin G (IgG)-by using a simple four-site model to mimic the shape of IgG. The interaction potential between the protein molecules consists of a Derjaguin-Landau-Verwey-Overbeek-type colloidal potential and an Asakura-Oosawa depletion potential arising from the addition of polymer. Liquid-liquid equilibria and fluid-solid equilibria are calculated by using the Gibbs ensemble Monte Carlo technique and the Gibbs-Duhem integration (GDI) method, respectively. Absolute Helmholtz energy is also calculated to get an initial coexisting point as required by GDI. The results reveal a nonmonotonic dependence of the critical polymer concentration rho(PEG) (*) (i.e., the minimum polymer concentration needed to induce liquid-liquid phase separation) on the polymer-to-protein size ratio q (equivalently, the range of the polymer-induced depletion interaction potential). We have developed a simple equation for estimating the minimum amount of polymer needed to induce the liquid-liquid phase separation and show that rho(PEG) (*) approximately [q(1+q)(3)]. The results also show that the liquid-liquid phase separation is metastable for low-molecular weight polymers (q=0.2) but stable at large molecular weights (q=1.0), thereby indicating that small sizes of polymer are required for protein crystallization. The simulation results provide practical guidelines for the selection of polymer size and ionic strength for protein phase separation and crystallization.

Improvement of glass-forming ability and phase separation in Cu Ti-rich

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

Park, E S; Chang, H J; Kim, D H

2010-01-01

Present study reports improvement of glass-forming ability (GFA) and phase separation in Cu Ti-rich Cu Ti Zr Ni Si bulk metallic glasses (BMGs) by tailoring the constituent elements. The MA of metalloid element, Sn having relatively large negative enthalpy of mixing can lead to improve GFA (up to 8mm in diameter) as well as thermal stability (up toTx = 48K) by optimizing the substitution element. And the addition of elements having relatively large positive enthalpy of mixing (partial substitution of Zr or Ti with Y) can lead to the liquid state phase separation in Cu Ti Sn Zr Ni Simore » BMG, although the addition lead to drastic deterioration of the GFA.« less

Superconductivity, phase separation, and charge-transfer instability in the U = infinity limit of the three-band model of the CuO sub 2 planes

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

Grilli, M.; Raimondi, R.; Castellani, C.

1991-07-08

The {ital U}={infinity} limit of the three-band Hubbard model with nearest-neighbor repulsion {ital V} is studied using the slave-boson approach and the large-{ital N} expansion technique to order 1/{ital N}. A charge-transfer instability is found as in weak-coupling theory. The charge-transfer instability is always associated with a diverging compressibility leading to a phase separation. Near the phase-separation, charge-transfer-instability region we find superconducting instabilities in the {ital s}- and {ital d}-wave channel. The requirement for superconductivity is that {ital V} be on the scale of the Cu-O hopping as suggested by Varma, Schmitt-Rink, and Abrahams.

SEPARATION OF HAZARDOUS ORGANICS BY LOW PRESSURE REVERSE OSMOSIS MEMBRANES - PHASE II FINAL REPORT

EPA Science Inventory

Extensive experimental studies showed that thin-film, composite membranes can be used effectively for the separation of selected hazardous organic compounds. This waste treatment technique offers definite advantages in terms of high solute separations at low pressures (<2MPa) and...

Correlated lateral phase separations in stacks of lipid membranes

NASA Astrophysics Data System (ADS)

Hoshino, Takuma; Komura, Shigeyuki; Andelman, David

2015-12-01

Motivated by the experimental study of Tayebi et al. [Nat. Mater. 11, 1074 (2012)] on phase separation of stacked multi-component lipid bilayers, we propose a model composed of stacked two-dimensional Ising spins. We study both its static and dynamical features using Monte Carlo simulations with Kawasaki spin exchange dynamics that conserves the order parameter. We show that at thermodynamical equilibrium, due to strong inter-layer correlations, the system forms a continuous columnar structure for any finite interaction across adjacent layers. Furthermore, the phase separation shows a faster dynamics as the inter-layer interaction is increased. This temporal behavior is mainly due to an effective deeper temperature quench because of the larger value of the critical temperature, Tc, for larger inter-layer interaction. When the temperature ratio, T/Tc, is kept fixed, the temporal growth exponent does not increase and even slightly decreases as a function of the increased inter-layer interaction.

LC separation of calcipotriol from its photodegradation products and protection possibilities using adjuvants.

PubMed

Cirunay, J J; Vander Heyden, Y; Plaizier-Vercammen, J

2001-08-01

Mobile phase optimization and reversed-phase column characteristics were used to separate photodegradation products from the parent compound, 24-cyclopropyl-9-,10-secochola-5,7,10(19),22-tetraene-1alpha,3beta,24-triol (calcipotriol). Separation between calcipotriol and its degradation products was obtained with an acetonitrile/water (53:47, v/v) mobile phase on a C(18) Hypersil ODS column (250 mm length, 4.6 mm id, 5 microm particle size) and a flow rate of 1 ml/min. Using this system, the influence of commonly used solvents in dermatology on degradation was studied. The addition of a UV filter in two concentrations was also evaluated for its possible protective effect to light exposure. Propylene glycol and polyethylene glycol 400 decreased the speed of degradation. The sunscreen 2-hydroxy-4-methoxybenzophenone affords a protection proportional to the filter concentration used in the study.

Resonant pairing between fermions with unequal masses

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

Wu, Shin-Tza; Pao, C.-H.; Yip, S.-K.

We study via mean-field theory the pairing between fermions of different masses, especially at the unitary limit. At equal populations, the thermodynamic properties are identical with the equal mass case provided an appropriate rescaling is made. At unequal populations, for sufficiently light majority species, the system does not phase separate. For sufficiently heavy majority species, the phase separated normal phase have a density larger than that of the superfluid. For atoms in harmonic traps, the density profiles for unequal mass fermions can be drastically different from their equal-mass counterparts.

Evidence of a miscibility gap in the FeTe1-xSex polycrystalline samples prepared with a melting process

NASA Astrophysics Data System (ADS)

Sala, A.; Palenzona, A.; Bernini, C.; Caglieris, F.; Cimberle, M. R.; Ferdeghini, C.; Lamura, G.; Martinelli, A.; Pani, M.; Hecher, J.; Eisterer, M.; Putti, M.

2014-05-01

The study of overdoped FeTe1-xSex (0.5 < x < 1) polycrystalline superconductor samples is reported. The samples were prepared using a melting technique previously developed by our group. Increasing the Se content a phase separation related to the formation of FeSe inside the Fe(Se,Te) phase happens, as demonstrated by structural analysis and magnetic characterization. The proposed phase separation picture is likely the fingerprint of a miscibility gap in the Fe(Se,Te) system.

Enantioseparation of Six Antihistamines with Immobilized Cellulose Chiral Stationary Phase by HPLC

PubMed Central

Zhou, Jie; Luo, Pei; Chen, Shanshan; Meng, Lingchang; Sun, Chong; Du, Qiuzheng; Sun, Fang

2016-01-01

A stereoselective high performance liquid chromatography method has been developed for the chiral separation of the enantiomers of six antihistamines, doxylamine, carbinoxamine, dioxopromethazine, oxomemazine, cetirizine and hydroxyzine. The effects of mobile phase additive, column temperature and flow rate on the retention time and resolution were studied. Enantiomeric separation of cetirizine, doxylamine and hydroxyzine were achieved on cellulose tris-(3,5-dichlorophenylcarbamate) immobilized on silica gel chiral stationary phase known as Chiralpak IC (RS = 3.74, RS = 1.85 and RS = 1.74, respectively). PMID:26657408

Computer simulation of phase separation under a double temperature quench.

PubMed

Podariu, Iulia; Chakrabarti, Amitabha

2007-04-21

The authors numerically study a two-step quench process in an asymmetric binary mixture. The mixture is first quenched to an unstable state in the two-phase region. After a large phase-separated structure is formed, the authors again quench the system deeper. The second quench induces the formation of small secondary droplets inside the large domains created by the first quench. The authors characterize this secondary droplet growth in terms of the temperature of the first quench as well as the depth of the second one.

Liquid Crystals in Chromatography

NASA Astrophysics Data System (ADS)

Witkiewicz, Zygfryd

The following sections are included: * INTRODUCTION * LIQUID CRYSTALS SUITABLE FOR GAS CHROMATOGRAPHY * Monomeric Liquid Crystal Stationary Phases * Polymeric Liquid Crystal Stationary Phases * Polymeric Liquid Crystal Stationary Phases * Conventional Analytical Columns * Capillary Columns * FACTORS AFFECTING THE CHROMATOGRAPHIC SEPARATIONS ON LIQUID CRYSTAL STATIONARY PHASES * Kind of Mesophase of the Liquid Crystal * Molecular Structure of the Liquid Crystals and of the Chromatographed Substances * Substrate on which the Liquid Crystal is Deposited * ANALYTICAL APPLICATIONS OF LIQUID CRYSTAL STATIONARY PHASES IN GAS CHROMATOGRAPHY * Separation of Isomers of Benzene and Naphthalene Derivatives * Separation of Alkane and Alkene Isomers * Separation of Mixtures of Benzene and Aliphatic Hydrocarbon Derivatives Containing Heteroatoms * Separation of Polynuclear Hydrocarbons * INVESTIGATION OF THE PROPERTIES OF LIQUID CRYSTALS BY GAS CHROMATOGRAPHY * APPLICATION OF LIQUID CRYSTALS IN LIQUID CHROMATOGRAPHY * Column Chromatography * Thin-Layer Chromatography * APPLICATION OF LIQUID CRYSTAL STATIONARY PHASES IN SUPERCRITICAL FLUID CHROMATOGRAPHY * FINAL REMARKS * References

Comparison of GC stationary phases for the separation of fatty acid methyl esters in biodiesel fuels.

PubMed

Goding, Julian C; Ragon, Dorisanne Y; O'Connor, Jack B; Boehm, Sarah J; Hupp, Amber M

2013-07-01

The fatty acid methyl ester (FAME) content of biodiesel fuels has traditionally been determined using gas chromatography with a polar stationary phase. In this study, a direct comparison of the separation of FAMEs present in various biodiesel samples on three polar stationary phases and one moderately polar stationary phase (with comparable column dimensions) was performed. Retention on each column was based on solubility in and polarity of the phase. Quantitative metrics describing the resolution of important FAME pairs indicate high resolution on all polar columns, yet the best resolution, particularly of geometric isomers, is achieved on the cyanopropyl column. In addition, the separation of four C18 monounsaturated isomers was optimized and the elution order determined on each column. FAME composition of various biodiesel fuel types was determined on each column to illustrate (1) chemical differences in biodiesels produced from different feedstocks and (2) chemical similarities in biodiesels of the same feedstock type produced in different locations and harvest seasons.

Phase separation and the formation of the pyrenoid, a carbon-fixing organelle

NASA Astrophysics Data System (ADS)

Xu, Bin; Freeman Rosenzweig, Elizabeth; Mackinder, Luke; Jonikas, Martin; Wingreen, Ned S.

In the chloroplasts of most algae, the carbon-fixing enzyme Rubisco is concentrated in a non-membrane-bound structure called the pyrenoid, which enables more efficient carbon capture than that of most land plants. In contrast to the long-held assumptions of the field, the pyrenoid matrix is not a solid crystal, but behaves as a phase-separated, liquid-like organelle. In this system, the linker protein EPYC1 is thought to form multivalent specific bonds with Rubisco, and the formation of the pyrenoid occurs via the phase separation of these two associating proteins. Through analytical and numerical studies, we determine a phase diagram for this system. We also show how the length of the linker protein can affect the formation and dissolution of the pyrenoid in an unexpected manner. This new view of the pyrenoid matrix provides important insights into the structure, regulation, and inheritance of pyrenoid. More broadly, our findings give insights into fundamental principles of the architecture and inheritance of liquid-phase organelles.

Sedimentation of a two-dimensional colloidal mixture exhibiting liquid-liquid and gas-liquid phase separation: a dynamical density functional theory study.

PubMed

Malijevský, Alexandr; Archer, Andrew J

2013-10-14

We present dynamical density functional theory results for the time evolution of the density distribution of a sedimenting model two-dimensional binary mixture of colloids. The interplay between the bulk phase behaviour of the mixture, its interfacial properties at the confining walls, and the gravitational field gives rise to a rich variety of equilibrium and non-equilibrium morphologies. In the fluid state, the system exhibits both liquid-liquid and gas-liquid phase separation. As the system sediments, the phase separation significantly affects the dynamics and we explore situations where the final state is a coexistence of up to three different phases. Solving the dynamical equations in two-dimensions, we find that in certain situations the final density profiles of the two species have a symmetry that is different from that of the external potentials, which is perhaps surprising, given the statistical mechanics origin of the theory. The paper concludes with a discussion on this.

Thermal cycling effects on static and dynamic properties of a phase separated manganite

NASA Astrophysics Data System (ADS)

Sacanell, J.; Sievers, B.; Quintero, M.; Granja, L.; Ghivelder, L.; Parisi, F.

2018-06-01

In this work we address the interplay between two phenomena which are signatures of the out-of-equilibrium state in phase separated manganites: irreversibility against thermal cycling and aging/rejuvenation process. The sample investigated is La0.5Ca0.5MnO3, a prototypical manganite exhibiting phase separation. Two regimes for isothermal relaxation were observed according to the temperature range: for T > 100 K, aging/rejuvenation effects are observed, while for T < 100 K an irreversible aging was found. Our results show that thermal cycles act as a tool to unveil the dynamical behavior of the phase separated state in manganites, revealing the close interplay between static and dynamic properties of phase separated manganites.

Phase transformation in SiOx/SiO₂ multilayers for optoelectronics and microelectronics applications.

PubMed

Roussel, M; Talbot, E; Pratibha Nalini, R; Gourbilleau, F; Pareige, P

2013-09-01

Due to the quantum confinement, silicon nanoclusters (Si-ncs) embedded in a dielectric matrix are of prime interest for new optoelectronics and microelectronics applications. In this context, SiO(x)/SiO₂ multilayers have been prepared by magnetron sputtering and subsequently annealed to induce phase separation and Si clusters growth. The aim of this paper is to study phase separation processes and formation of nanoclusters in SiO(x)/SiO₂ multilayers by atom probe tomography. Influences of the silicon supersaturation, annealing temperature and SiO(x) and SiO₂ layer thicknesses on the final microstructure have been investigated. It is shown that supersaturation directly determines phase separation regime between nucleation/classical growth and spinodal decomposition. Annealing temperature controls size of the particles and interface with the surrounding matrix. Layer thicknesses directly control Si-nc shapes from spherical to spinodal-like structures. Copyright © 2012 Elsevier B.V. All rights reserved.

Manipulating electronic phase separation in strongly correlated oxides with an ordered array of antidots

DOE PAGES

Zhang, Kai; Du, Kai; Liu, Hao; ...

2015-07-20

The interesting transport and magnetic properties in manganites depend sensitively on the nucleation and growth of electronic phase-separated domains. In this paper, by fabricating antidot arrays in La 0.325Pr 0.3Ca 0.375MnO 3 (LPCMO) epitaxial thin films, we create ordered arrays of micrometer-sized ferromagnetic metallic (FMM) rings in the LPCMO films that lead to dramatically increased metal–insulator transition temperatures and reduced resistances. The FMM rings emerge from the edges of the antidots where the lattice symmetry is broken. Based on our Monte Carlo simulation, these FMM rings assist the nucleation and growth of FMM phase domains increasing the metal–insulator transition withmore » decreasing temperature or increasing magnetic field. Finally, this study points to a way in which electronic phase separation in manganites can be artificially controlled without changing chemical composition or applying external field.« less

Stress-Triggered Phase Separation Is an Adaptive, Evolutionarily Tuned Response

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

Riback, Joshua A.; Katanski, Christopher D.; Kear-Scott, Jamie L.

In eukaryotic cells, diverse stresses trigger coalescence of RNA-binding proteins into stress granules. In vitro, stress-granule-associated proteins can demix to form liquids, hydrogels, and other assemblies lacking fixed stoichiometry. Observing these phenomena has generally required conditions far removed from physiological stresses. We show that poly(A)-binding protein (Pab1 in yeast), a defining marker of stress granules, phase separates and forms hydrogels in vitro upon exposure to physiological stress conditions. Other RNA-binding proteins depend upon low-complexity regions (LCRs) or RNA for phase separation, whereas Pab1’s LCR is not required for demixing, and RNA inhibits it. Based on unique evolutionary patterns, we createmore » LCR mutations, which systematically tune its biophysical properties and Pab1 phase separation in vitro and in vivo. Mutations that impede phase separation reduce organism fitness during prolonged stress. Poly(A)-binding protein thus acts as a physiological stress sensor, exploiting phase separation to precisely mark stress onset, a broadly generalizable mechanism.« less

Method for separating water soluble organics from a process stream by aqueous biphasic extraction

DOEpatents

Chaiko, David J.; Mego, William A.

1999-01-01

A method for separating water-miscible organic species from a process stream by aqueous biphasic extraction is provided. An aqueous biphase system is generated by contacting a process stream comprised of water, salt, and organic species with an aqueous polymer solution. The organic species transfer from the salt-rich phase to the polymer-rich phase, and the phases are separated. Next, the polymer is recovered from the loaded polymer phase by selectively extracting the polymer into an organic phase at an elevated temperature, while the organic species remain in a substantially salt-free aqueous solution. Alternatively, the polymer is recovered from the loaded polymer by a temperature induced phase separation (cloud point extraction), whereby the polymer and the organic species separate into two distinct solutions. The method for separating water-miscible organic species is applicable to the treatment of industrial wastewater streams, including the extraction and recovery of complexed metal ions from salt solutions, organic contaminants from mineral processing streams, and colorants from spent dye baths.

Construction of a hydrazone-linked chiral covalent organic framework-silica composite as the stationary phase for high performance liquid chromatography.

PubMed

Zhang, Kai; Cai, Song-Liang; Yan, Yi-Lun; He, Zi-Hao; Lin, Hui-Mei; Huang, Xiao-Ling; Zheng, Sheng-Run; Fan, Jun; Zhang, Wei-Guang

2017-10-13

Covalent organic frameworks (COFs), as an emerging class of crystalline porous organic polymers, have great potential for applications in chromatographic separation owning to their fascinating crystalline structures and outstanding properties. However, development of COF materials as novel stationary phases in high performance liquid chromatography (HPLC) is just in its infancy. Herein, we report the design and construction of a new hydrazone-linked chiral COF, termed BtaMth COF, from a chiral hydrazide building block (Mth) and present a one-pot synthetic method for the fabrication of BtaMth@SiO 2 composite for HPLC separation of isomers. The as-synthesized BtaMth chiral COF displays good crystallinity, high porosity, as well as excellent chemical stability. Meanwhile, the fabricated HPLC column by using BtaMth@SiO 2 composite as the new stationary phase exhibits high resolution performances for the separation of positional isomers including nitrotoluene and nitrochlorobenzene, as well as cis-trans isomers including beta-cypermethrin and metconazole. Additionally, some effects such as the composition of the mobile phase and column temperature for HPLC separations on the BtaMth@SiO 2 packed column also have been studied in detail. The successful applications indicate the great potentials of hydrazone-linked chiral COF-silica composite as novel stationary phase for the efficient HPLC separation. Copyright © 2017 Elsevier B.V. All rights reserved.

Fundamental Physics

NASA Image and Video Library

2003-01-22

Still photographs taken over 16 hours on Nov. 13, 2001, on the International Space Station have been condensed into a few seconds to show the de-mixing -- or phase separation -- process studied by the Experiment on Physics of Colloids in Space. Commanded from the ground, dozens of similar tests have been conducted since the experiment arrived on ISS in 2000. The sample is a mix of polymethylmethacrylate (PMMA or acrylic) colloids, polystyrene polymers and solvents. The circular area is 2 cm (0.8 in.) in diameter. The phase separation process occurs spontaneously after the sample is mechanically mixed. The evolving lighter regions are rich in colloid and have the structure of a liquid. The dark regions are poor in colloids and have the structure of a gas. This behavior carnot be observed on Earth because gravity causes the particles to fall out of solution faster than the phase separation can occur. While similar to a gas-liquid phase transition, the growth rate observed in this test is different from any atomic gas-liquid or liquid-liquid phase transition ever measured experimentally. Ultimately, the sample separates into colloid-poor and colloid-rich areas, just as oil and vinegar separate. The fundamental science of de-mixing in this colloid-polymer sample is the same found in the annealing of metal alloys and plastic polymer blends. Improving the understanding of this process may lead to improving processing of these materials on Earth.

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

Amitava Sarkar; James K. Neathery; Burtron H. Davis

A fundamental filtration study was started to investigate the separation of Fischer-Tropsch Synthesis (FTS) liquids from iron-based catalyst particles. Slurry-phase FTS in slurry bubble column reactor systems is the preferred mode of operation since the reaction is highly exothermic. Consequently, heavy wax products in one approach may be separated from catalyst particles before being removed from the reactor system. Achieving an efficient wax product separation from iron-based catalysts is one of the most challenging technical problems associated with slurry-phase iron-based FTS and is a key factor for optimizing operating costs. The separation problem is further compounded by attrition of ironmore » catalyst particles and the formation of ultra-fine particles.« less

Separation and Recovery of a Hemicellulose-Derived Sugar Produced from the Hydrolysis of Biomass by an Acidic Ionic Liquid.

PubMed

da Costa Lopes, Andre M; Łukasik, Rafał M

2018-03-22

Biomass processing with ionic liquids (ILs) has been one of the most topical research areas in recent years. However, separation and recovery of biomass products and ILs are currently a challenge. Recovery of produced monosaccharides from an IL postreaction solution and the possibility to reuse the IL are strongly required to guarantee the sustainability of biomass processing. The present study demonstrates a novel approach that aims at separating a biomass hemicellulose-derived product, namely, xylose, and 1-ethyl-3-methylimidazolium hydrogensulfate ([emim][HSO 4 ]). High polarity of a postreaction system composed of xylose, IL, and water is one of the major hindrances in the separation performance. A proposed solution is fine-tuning of the system polarity by the addition of moderately polar acetonitrile. To scrutinize the potential of xylose and IL separation, phase equilibria of a system constituted by [emim][HSO 4 ], water, and acetonitrile were studied. Additionally, preparative chromatography experiments with alumina as a stationary phase were performed to determine the conditions required for efficient separation of the sugar and the IL by selective adsorption of xylose on alumina in detriment of IL. The amount and treatment of the stationary phase, eluent polarity, and amount of loaded sample were also scrutinized in this study. Treatment of alumina was considered as a necessary step to achieve recovery yields of 90.8 and 98.1 wt % for the IL and xylose, respectively, as separate fractions. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Process for improving soluble coal yield in a coal deashing process

DOEpatents

Rhodes, Donald E.

1980-01-01

Coal liquefaction products are contacted with a deashing solvent and introduced into a first separation zone. The first separation zone is maintained at an elevated temperature and pressure, determined to maximize the recovery of soluble coal products, to cause said coal liquefaction products to separate into a first light phase and a first heavy phase. Under these conditions the heavy phase while still fluid-like in character is substantially non-flowable. Flowability is returned to the fluid-like heavy phase by the introduction of an additional quantity of deashing solvent into the first separation zone at a location below the interface between the first light and heavy phases or into the heavy phase withdrawal conduit during withdrawal of the first heavy phase and prior to any substantial pressure reduction. The first heavy phase then is withdrawn from the first separation zone for additional downstream processing without plugging either the withdrawal conduit or the downstream apparatus. The first light phase comprising the soluble coal products is withdrawn and recovered in an increased yield to provide a more economical coal deashing process.

Physiological Differences in the Follicular, Luteal, and Menstrual Phases in Healthy Women Determined by Electrovestibulography: Depression, Anxiety, or Other Associations?

PubMed

Lithgow, Brian J; Moussavi, Zahra

2018-06-05

Electrovestibulography (EVestG) recordings have been previously applied toward classifying and/or measuring the severity of several neurological disorders including depression with and without anxiety. This study's objectives were to: (1) extract EVestG features representing physiological differences of healthy women during their menses, and follicular and luteal phases of their menstrual cycle, and (2) compare these features to those observed in previous studies for depression with and without anxiety. Three EVestG recordings were made on 15 young healthy menstruating females during menses, and follicular and luteal phases. Three features were extracted, using the shape and timing of the detected spontaneously evoked vestibulo-acoustic field potentials. Using these features, a 3-way separation of the 3 phases was achieved, with a leave-one-out cross-validation, resulting in accuracy of > 72%. Using an EVestG shape feature, separation of the follicular and luteal phases was achieved with a leave-one-out cross-validation accuracy of > 93%. The mechanism of separation was not like that in previous depression analyses, and is postulated to be more akin to a form of anxiety and/or progesterone sensitivity. © 2018 S. Karger AG, Basel.

Distribution of free and antibody-bound peptide hormones in two-phase aqueous polymer systems

PubMed Central

Desbuquois, Bernard; Aurbach, G. D.

1972-01-01

Peptide hormones labelled with radioactive iodine were partitioned into the aqueous two-phase polymer systems developed by Albertsson (1960) and the conditions required for separation of free from antibody-bound hormone have been worked out. Hormones studied included insulin, growth hormone, parathyroid hormone and [arginine]-vasopressin. Free and antibody-bound hormones show different distribution coefficients in a number of systems tested; two systems, the dextran–polyethylene glycol and dextran sulphate–polyethylene glycol system, give optimum separation. Free hormones distribute readily into the upper phase of these systems, whereas hormone–antibody complexes, as well as uncombined antibody, are found almost completely in the lower phase. Various factors including the polymer concentration, the ionic composition of the system, the nature of the hormone and the nature of added serum protein differentially affect the distribution coefficients for free and antibody-bound hormone. These factors can be adequately controlled so as to improve separation. The two-phase partition method has been successfully applied to measure binding of labelled hormone to antibody under standard radioimmunoassay conditions. It exhibits several advantages over the method of equilibration dialysis and can be applied to the study of non-immunological interactions. PMID:4672674

Solidification studies of nanocrystalline and quasicrystalline materials from the undercooled state

NASA Astrophysics Data System (ADS)

Croat, Thomas Kevin

2001-07-01

Nanocrystallization occurring during metallic glass devitrification is studied in Zr-Al-Ni-Cu bulk metallic glasses (BMGs) and Al-RE-TM (RE = rare-earth, TM = transition metal) metallic glasses. The importance of transient nucleation in BMG devitrification was established by a direct transmission electron microscopy (TEM) measurement of the grain density in two-stage annealed samples. TEM examination of low temperature annealed BMGs also suggest that amorphous phase separation is occurring prior to crystallization. Nanocrystallization of rapidly quenched Al-RE-Ni glasses was preceded by the compositional segregation of the initially homogeneous glass into Al-rich and solute-rich regions (mainly nickel-enriched) on a ≈50--100 nm length scale, suggesting amorphous phase separation. This pre-existing compositional modulation on a nanometer scale leads naturally to the development of nanocrystals. The average rare earth radius (rRE) in Al-RE-Ni alloys was altered by co-substitution of chemically similar rare earth elements. In glasses with smaller r RE, nucleation of alpha-Al occurred preferentially near the boundaries of the phase-separated regions. However, phase separation did not universally lead to alpha-Al nanocrystallization; glasses with larger rRE crystallized to metastable intermetallic phases with a 50--100 nm grain size. Kinetic analysis of the alpha-Al crystallization was performed using isothermal DSC, yielding abnormally low Avrami exponents (n = 1.0--1.5); these values were found to be consistent with the observed transformation using a model that considers the overlapping diffusion fields of the alpha-Al grains during growth within the phase separated region. Containerless solidification experiments on Ti-based quasicrystal-forming alloys have been performed using various techniques, including drop-tube solidification, electromagnetic levitation (EML) and electrostatic levitation (ESL). In Ti-Fe-Si-O, the alpha-1/1 quasicrystal approximant phase is found to nucleate directly from the liquid over the range TixFe94-xSi 4(SiO2)2 with 67 < x < 69 in EML experiments. Both the alpha-1/1 phase in Ti-Fe-Si-O and the C14 Laves phase in Ti-Zr-Ni have lower relative undercoolings than nearby crystal phases. This presumably reflects the structural similarity between these polytetrahedral phases and the undercooled liquid, which leads to smaller nucleation barriers and lower maximum undercoolings.

Qualitative analysis of mycotoxins using micellar electrokinetic capillary chromatography

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

Holland, R.D.; Sepaniak, M.J.

1993-05-01

Naturally occurring mycotoxins are separated using micellar electrokinetic capillary chromatography. Trends in the retention of these toxins, resulting from changes in mobile-phase composition and pH, are reported and presented as a means of alleviating coelution problems. Two sets of mobile-phase conditions are determined that provide unique separation selectivity. The facile manner by which mobile-phase conditions can be altered, without changes in instrumental configuration, allowed the acquisition of two distinctive, fully resolved chromatograms of 10 mycotoxins in a period of approximately 45 min. By adjusting retention times, using indigenous or added components in mycotoxin samples as normalization standards, it is possiblemore » to obtain coefficients of variation in retention time that average less than 1%. The qualitative capabilities of this methodology are evaluated by separating randomly generated mycotoxin-interferent mixtures. In this study, the utilization of normalized retention times applied to separations obtained with two sets of mobile-phase conditions permitted the identification of all the mycotoxins in five unknown samples without any misidentifications. 24 refs., 3 figs., 2 tabs.« less

Liquid-liquid phase separation and core-shell structure of ternary Al-In-Sn immiscible alloys

NASA Astrophysics Data System (ADS)

Zhao, Degang; Bo, Lin; Wang, Lin; Li, Shanshan

2018-04-01

In this study, the liquid-liquid phase separation of four kinds of ternary immiscible Al-In-Sn melts was investigated with resistivity and thermodynamics method. The nonlinear changes in ρ-T and DSC curves of Al-In-Sn immiscible alloys above monotectic reaction temperature revealed the occurrence of liquid-liquid phase separation of Al-In-Sn melts. The monotectic temperature, liquid phase separation temperature and immiscible gap of ternary Al-In-Sn alloys were lower than those of binary Al-In alloy. With the Al content decreasing, the immiscible gap of Al-In-Sn alloy decreased. The composition of Al80In10Sn10, Al70In15Sn15, Al60In20Sn20 and Al50In25Sn25 was located in the immiscible zone of Al-In-Sn system. Due to the differences of Stokes effect, Marangoni convection and immiscible gap, the solidification morphology of four kinds of Al-In-Sn monotectic alloy was different. The core–shell structure of Al-In-Sn monotectic alloy can form within a certain range of composition.

Continuously phase-modulated standing surface acoustic waves for separation of particles and cells in microfluidic channels containing multiple pressure nodes

NASA Astrophysics Data System (ADS)

Lee, Junseok; Rhyou, Chanryeol; Kang, Byungjun; Lee, Hyungsuk

2017-04-01

This paper describes continuously phase-modulated standing surface acoustic waves (CPM-SSAW) and its application for particle separation in multiple pressure nodes. A linear change of phase in CPM-SSAW applies a force to particles whose magnitude depends on their size and contrast factors. During continuous phase modulation, we demonstrate that particles with a target dimension are translated in the direction of moving pressure nodes, whereas smaller particles show oscillatory movements. The rate of phase modulation is optimized for separation of target particles from the relationship between mean particle velocity and period of oscillation. The developed technique is applied to separate particles of a target dimension from the particle mixture. Furthermore, we also demonstrate human keratinocyte cells can be separated in the cell and bead mixture. The separation technique is incorporated with a microfluidic channel spanning multiple pressure nodes, which is advantageous over separation in a single pressure node in terms of throughput.

Selective Detection of Peptide-Oligonucleotide Heteroconjugates Utilizing Capillary HPLC-ICPMS

NASA Astrophysics Data System (ADS)

Catron, Brittany; Caruso, Joseph A.; Limbach, Patrick A.

2012-06-01

A method for the selective detection and quantification of peptide:oligonucleotide heteroconjugates, such as those generated by protein:nucleic acid cross-links, using capillary reversed-phase high performance liquid chromatography (cap-RPHPLC) coupled with inductively coupled plasma mass spectrometry detection (ICPMS) is described. The selective detection of phosphorus as 31P+, the only natural isotope, in peptide-oligonucleotide heteroconjugates is enabled by the elemental detection capabilities of the ICPMS. Mobile phase conditions that allow separation of heteroconjugates while maintaining ICPMS compatibility were investigated. We found that trifluoroacetic acid (TFA) mobile phases, used in conventional peptide separations, and hexafluoroisopropanol/triethylamine (HFIP/TEA) mobile phases, used in conventional oligonucleotide separations, both are compatible with ICPMS and enable heteroconjugate separation. The TFA-based separations yielded limits of detection (LOD) of ~40 ppb phosphorus, which is nearly seven times lower than the LOD for HFIP/TEA-based separations. Using the TFA mobile phase, 1-2 pmol of a model heteroconjugate were routinely separated and detected by this optimized capLC-ICPMS method.

Images reveal that atmospheric particles can undergo liquid–liquid phase separations

PubMed Central

You, Yuan; Renbaum-Wolff, Lindsay; Carreras-Sospedra, Marc; Hanna, Sarah J.; Hiranuma, Naruki; Kamal, Saeid; Smith, Mackenzie L.; Zhang, Xiaolu; Weber, Rodney J.; Shilling, John E.; Dabdub, Donald; Martin, Scot T.; Bertram, Allan K.

2012-01-01

A large fraction of submicron atmospheric aerosol particles contains both organic material and inorganic salts. As the relative humidity cycles in the atmosphere and the water content of the particles correspondingly changes, these mixed particles can undergo a range of phase transitions, possibly including liquid–liquid phase separation. If liquid–liquid phase separation occurs, the gas-particle partitioning of atmospheric semivolatile organic compounds, the scattering and absorption of solar radiation, and the reactive uptake of gas species on atmospheric particles may be affected, with important implications for climate predictions. The actual occurrence of liquid–liquid phase separation within individual atmospheric particles has been considered uncertain, in large part because of the absence of observations for real-world samples. Here, using optical and fluorescence microscopy, we present images that show the coexistence of two noncrystalline phases for real-world samples collected on multiple days in Atlanta, GA as well as for laboratory-generated samples under simulated atmospheric conditions. These results reveal that atmospheric particles can undergo liquid–liquid phase separations. To explore the implications of these findings, we carried out simulations of the Atlanta urban environment and found that liquid–liquid phase separation can result in increased concentrations of gas-phase NO3 and N2O5 due to decreased particle uptake of N2O5. PMID:22847443

Images reveal that atmospheric particles can undergo liquid-liquid phase separations.

PubMed

You, Yuan; Renbaum-Wolff, Lindsay; Carreras-Sospedra, Marc; Hanna, Sarah J; Hiranuma, Naruki; Kamal, Saeid; Smith, Mackenzie L; Zhang, Xiaolu; Weber, Rodney J; Shilling, John E; Dabdub, Donald; Martin, Scot T; Bertram, Allan K

2012-08-14

A large fraction of submicron atmospheric aerosol particles contains both organic material and inorganic salts. As the relative humidity cycles in the atmosphere and the water content of the particles correspondingly changes, these mixed particles can undergo a range of phase transitions, possibly including liquid-liquid phase separation. If liquid-liquid phase separation occurs, the gas-particle partitioning of atmospheric semivolatile organic compounds, the scattering and absorption of solar radiation, and the reactive uptake of gas species on atmospheric particles may be affected, with important implications for climate predictions. The actual occurrence of liquid-liquid phase separation within individual atmospheric particles has been considered uncertain, in large part because of the absence of observations for real-world samples. Here, using optical and fluorescence microscopy, we present images that show the coexistence of two noncrystalline phases for real-world samples collected on multiple days in Atlanta, GA as well as for laboratory-generated samples under simulated atmospheric conditions. These results reveal that atmospheric particles can undergo liquid-liquid phase separations. To explore the implications of these findings, we carried out simulations of the Atlanta urban environment and found that liquid-liquid phase separation can result in increased concentrations of gas-phase NO(3) and N(2)O(5) due to decreased particle uptake of N(2)O(5).

Self-referenced locking of optical coherence by single-detector electronic-frequency tagging

NASA Astrophysics Data System (ADS)

Shay, T. M.; Benham, Vincent; Spring, Justin; Ward, Benjamin; Ghebremichael, F.; Culpepper, Mark A.; Sanchez, Anthony D.; Baker, J. T.; Pilkington, D.; Berdine, Richard

2006-02-01

We report a novel coherent beam combining technique. This is the first actively phase locked optical fiber array that eliminates the need for a separate reference beam. In addition, only a single photodetector is required. The far-field central spot of the array is imaged onto the photodetector to produce the phase control loop signals. Each leg of the fiber array is phase modulated with a separate RF frequency, thus tagging the optical phase shift for each leg by a separate RF frequency. The optical phase errors for the individual array legs are separated in the electronic domain. In contrast with the previous active phase locking techniques, in our system the reference beam is spatially overlapped with all the RF modulated fiber leg beams onto a single detector. The phase shift between the optical wave in the reference leg and in the RF modulated legs is measured separately in the electronic domain and the phase error signal is feedback to the LiNbO 3 phase modulator for that leg to minimize the phase error for that leg relative to the reference leg. The advantages of this technique are 1) the elimination of the reference beam and beam combination optics and 2) the electronic separation of the phase error signals without any degradation of the phase locking accuracy. We will present the first theoretical model for self-referenced LOCSET and describe experimental results for a 3 x 3 array.

Brief Report: Atypical Expression of Distress during the Separation Phase of the Strange Situation Procedure in Infant Siblings at High Risk for ASD

ERIC Educational Resources Information Center

Esposito, Gianluca; del Carmen Rostagno, Maria; Venuti, Paola; Haltigan, John D.; Messinger, Daniel S.

2014-01-01

Previous studies have provided preliminary evidence that disruptions in cry acoustics may be part of an atypical vocal signature of autism early in life. We examined the acoustic characteristics of cries extracted from the separation phase of the strange situation procedure in a sample of toddler of younger siblings of a child with autism spectrum…

Changes of buoyant density during the S-phase of the cell cycle. Direct evidence demonstrated in acute myeloid leukemia by flowcytometry.

PubMed

Daenen, S; Huiges, W; Modderman, E; Halie, M R

1993-01-01

Studies with synchronized or exponentially growing bacteria and mammalian cell lines are not able to demonstrate small changes in buoyant density during the cell cycle. Flowcytometric analysis of density separated acute myeloid leukemia cells, a system not dependent on time-related variables, shows that the cellular buoyant density increases slightly with up to 0.008 g/ml during the S-phase, at least in cryo-preserved cells used in this study. This contrasts with the generally accepted belief that S-phase cells have a lower or constant buoyant density. A practical implication is that separation of cell (sub)populations based on differences in buoyant density could be flawed to the extent that these populations contain S-phase cells.

Numerical study of particle deposition and scaling in dust exhaust of cyclone separator

NASA Astrophysics Data System (ADS)

Xu, W. W.; Li, Q.; Zhao, Y. L.; Wang, J. J.; Jin, Y. H.

2016-05-01

The solid particles accumulation in the dust exhaust cone area of the cyclone separator can cause the wall wear. This undoubtedly prevents the flue gas turbine from long period and safe operation. So it is important to study the mechanism how the particles deposited and scale on dust exhaust cone area of the cyclone separator. Numerical simulations of gas-solid flow field have been carried out in a single tube in the third cyclone separator. The three-dimensionally coupled computational fluid dynamic (CFD) technology and the modified Discrete Phase Model (DPM) are adopted to model the gas-solid two-phase flow. The results show that with the increase of the operating temperature and processing capacity, the particle sticking possibility near the cone area will rise. The sticking rates will decrease when the particle diameter becomes bigger.

Improved separation with the intermittently pressed tubing of multilayer coil in type-I counter-current chromatography.

PubMed

Yang, Yi; Yang, Jiao; Fang, Chen; Wang, Jihui; Gu, Dongyu; Tian, Jing; Ito, Yoichiro

2018-05-25

The intermittently pressed tubing was introduced in type-I counter-current chromatographic system as the separation column to improve the separation performance in the present study. The separations were performed with two different solvent systems composed of 1-butanol-acetic acid-water (4:1:5, v/v) (BAW) and hexane-ethyl acetate-methanol-0.1 M HCl (1:1:1:1, v/v) (HEMW) using dipeptides and DNP-amino acids as test samples, respectively. The chromatographic performance was evaluated in terms of retention of the stationary phase (Sf), theoretical plate (N) and peak resolution (Rs). In general, the type-I planetary motion with the multilayer coil of non-modified standard tubing can yield the best separation at a low revolution speed of 200 rpm with lower flow rate. The present results with intermittently pressed tubing indicated that the performance was also optimal at the revolution speed of 200 rpm where the lower flow rate was more beneficial to retention of stationary phase and resolution. In the moderately hydrophobic two-phase solvent system composed of hexane-ethyl acetate-metanol-0.1 M hydrochloric acid (1:1:1:1, v/v), DNP-amino acids were separated with Rs at 1.67 and 1.47, respectively, with 12.66% of stationary phase retention at a flow rate of 0.25 ml/min. In the polar solvent system composed of 1-butanol-acetic acid-water (4:1:5, v/v), dipeptide samples were resolved with Rs at 2.18 and 18.75% of stationary phase retention at a flow rate of 0.25 ml/min. These results indicate that the present system substantially improves the separation efficiency of type-I counter-current chromatographic system. Published by Elsevier B.V.

Improved Separations of Proteins and Sugar Derivatives Using the Small-Scale Cross-Axis Coil Planet Centrifuge with Locular Multilayer Coiled Columns.

PubMed

Shinomiya, Kazufusa; Umezawa, Motoki; Seki, Manami; Nitta, Jun; Zaima, Kazumasa; Harikai, Naoki; Ito, Yoichiro

2016-12-01

Countercurrent chromatography (CCC) is liquid-liquid partition chromatography without using a solid support matrix. This technique requires further improvement of partition efficiency and shortening theseparation time. The locular multilayer coils modified with and without mixer glass beads were developed for the separation of proteins and 4-methylumbelliferyl (MU) sugar derivatives using the small-scale cross-axis coil planet centrifuge. Proteins were well separated from each other and the separation was improved at a low flow rate of the mobile phase. On the other hand, 4-MU sugar derivatives were sufficiently resolved with short separation time at a highflow rate of the mobile phase under satisfactory stationary phase retention. Effective separations were achieved using the locular multilayer coil for proteins with aqueous-aqueous polymer phase systems and for 4-MU sugar derivatives with organic-aqueous two-phase solvent systems by inserting a glass bead into each locule.

Retention and effective diffusion of model metabolites on porous graphitic carbon.

PubMed

Lunn, Daniel B; Yun, Young J; Jorgenson, James W

2017-12-29

The study of metabolites in biological samples is of high interest for a wide range of biological and pharmaceutical applications. Reversed phase liquid chromatography is a common technique used for the separation of metabolites, but it provides little retention for polar metabolites. An alternative to C18 bonded phases, porous graphitic carbon has the ability to provide significant retention for both non-polar and polar analytes. The goal of this work is to study the retention and effective diffusion properties of porous graphitic carbon, to see if it is suitable for the wide injection bands and long run times associated with long, packed capillary-scale separations. The retention of a set of standard metabolites was studied for both stationary phases over a wide range of mobile phase conditions. This data showed that porous graphitic carbon benefits from significantly increased retention (often >100 fold) under initial gradient conditions for these metabolites, suggesting much improved ability to focus a wide injection band at the column inlet. The effective diffusion properties of these columns were studied using peak-parking experiments with the standard metabolites under a wide range of retention conditions. Under the high retention conditions, which can be associated with retention after injection loading for gradient separations, D eff /D m ∼0.1 for both the C18-bonded and porous graphitic carbon columns. As C18 bonded particles are widely, and successfully utilized for long gradient separations without issue of increasing peak width from longitudinal diffusion, this suggests that porous graphitic carbon should be amenable for long runtime gradient separations as well. Copyright © 2017 Elsevier B.V. All rights reserved.

Enantiomeric separation of 2-arylpropionic acid nonsteroidal anti-inflammatory drugs by HPLC with hydroxypropyl-beta-cyclodextrin as chiral mobile phase additive.

PubMed

Ye, Jincui; Yu, Wenying; Chen, Guosheng; Shen, Zhengrong; Zeng, Su

2010-08-01

The enantio-separations of eight 2-arylpropionic acid nonsteroidal anti-inflammatory drugs (2-APA NSAIDs) were established using reversed-phase high-performance liquid chromatography with hydroxypropyl-beta-cyclodextrin (HP-beta-CD) as chiral mobile phase additive for studying the stereoselective skin permeation of suprofen, ketoprofen, naproxen, indoprofen, fenoprofen, furbiprofen, ibuprofen and carprofen. The effects of the mobile phase composition, concentration of HP-beta-CD and column temperature on retention and enantioselective separation were investigated. With 2-APA NSAIDs as acidic analytes, the retention times and resolutions of the enantiomers were strongly related to the pH of the mobile phase. In addition, both the concentration of HP-beta-CD and temperature had a great effect on retention time, but only a slight or almost no effect on resolutions of the analytes. Enantioseparations were achieved on a Shimpack CLC-ODS (150 x 4.6 mm i.d., 5 microm) column. The mobile phase was a mixture of methanol and phosphate buffer (pH 4.0-5.5, 20 mM) containing 25 mM HP-beta-CD. This method was flexible, simple and economically advantageous over the use of chiral stationary phase, and was successfully applied to the enantioselective determination of the racemic 2-APA NSAIDs in an enantioselective skin permeation study.

Ultrafast Dynamics in Vanadium Dioxide: Separating Spatially Segregated Mixed Phase Dynamics in the Time-domain

NASA Astrophysics Data System (ADS)

Hilton, David

2011-10-01

In correlated electronic systems, observed electronic and structural behavior results from the complex interplay between multiple, sometimes competing degrees-of- freedom. One such material used to study insulator-to-metal transitions is vanadium dioxide, which undergoes a phase transition from a monoclinic-insulating phase to a rutile-metallic phase when the sample is heated to 340 K. The major open question with this material is the relative influence of this structural phase transition (Peirels transition) and the effects of electronic correlations (Mott transition) on the observed insulator-to-metal transition. Answers to these major questions are complicated by vanadium dioxide's sensitivity to perturbations in the chemical structure in VO2. For example, related VxOy oxides with nearly a 2:1 ratio do not demonstrate the insulator-to- metal transition, while recent work has demonstrated that W:VO2 has demonstrated a tunable transition temperature controllable with tungsten doping. All of these preexisting results suggest that the observed electronic properties are exquisitely sensitive to the sample disorder. Using ultrafast spectroscopic techniques, it is now possible to impulsively excite this transition and investigate the photoinduced counterpart to this thermal phase transition in a strongly nonequilibrium regime. I will discuss our recent results studying the terahertz-frequency conductivity dynamics of this photoinduced phase transition in the poorly understood near threshold temperature range. We find a dramatic softening of the transition near the critical temperature, which results primarily from the mixed phase coexistence near the transition temperature. To directly study this mixed phase behavior, we directly study the nucleation and growth rates of the metallic phase in the parent insulator using non-degenerate optical pump-probe spectroscopy. These experiments measure, in the time- domain, the coexistent phase separation in VO2 (spatially separated insulator and metal islands) and, more importantly, their dynamic evolution in response to optical excitation.

Formation of porous crystals via viscoelastic phase separation

NASA Astrophysics Data System (ADS)

Tsurusawa, Hideyo; Russo, John; Leocmach, Mathieu; Tanaka, Hajime

2017-10-01

Viscoelastic phase separation of colloidal suspensions can be interrupted to form gels either by glass transition or by crystallization. With a new confocal microscopy protocol, we follow the entire kinetics of phase separation, from homogeneous phase to different arrested states. For the first time in experiments, our results unveil a novel crystallization pathway to sponge-like porous crystal structures. In the early stages, we show that nucleation requires a structural reorganization of the liquid phase, called stress-driven ageing. Once nucleation starts, we observe that crystallization follows three different routes: direct crystallization of the liquid phase, the Bergeron process, and Ostwald ripening. Nucleation starts inside the reorganized network, but crystals grow past it by direct condensation of the gas phase on their surface, driving liquid evaporation, and producing a network structure different from the original phase separation pattern. We argue that similar crystal-gel states can be formed in monatomic and molecular systems if the liquid phase is slow enough to induce viscoelastic phase separation, but fast enough to prevent immediate vitrification. This provides a novel pathway to form nanoporous crystals of metals and semiconductors without dealloying, which may be important for catalytic, optical, sensing, and filtration applications.

Cold-induced aqueous acetonitrile phase separation: A salt-free way to begin quick, easy, cheap, effective, rugged, safe.

PubMed

Shao, Gang; Agar, Jeffrey; Giese, Roger W

2017-07-14

Cooling a 1:1 (v/v) solution of acetonitrile and water at -16° C is known to result in two clear phases. We will refer to this event as "cold-induced aqueous acetonitrile phase separation (CIPS)". On a molar basis, acetonitrile is 71.7% and 13.6% in the upper and lower phases, respectively, in our study. The phase separation proceeds as a descending cloud of microdroplets. At the convenient temperature (typical freezer) employed here the lower phase is rather resistant to solidification, although it emerges from the freezer as a solid if various insoluble matter is present at the outset. In a preliminary way, we replaced the initial (salting-out) step of a representative QuEChERS procedure with CIPS, applying this modified procedure ("CIPS-QuEChERS") to a homogenate of salmon (and partly to beef). Three phases resulted, where only the upper, acetonitrile-rich phase is a liquid (that is completely clear). The middle phase comprises ice and precipitated lipids, while the lower phase is the residual matrix of undissolved salmon or meat. Treating the upper phase from salmon, after isolation, with anhydrous MgSO 4 and C18-Si (typical QuEChERS dispersive solid phase extraction sorbents), and injecting into a GC-MS in a nontargeted mode, gives two-fold more preliminary hits for chemicals, and also number of spiked pesticides recovered, relative to that from a comparable QuEChERS method. In part, this is because of much higher background signals in the latter case. Further study of CIPS-QuEChERS is encouraged, including taking advantage of other QuERChERS conditions. Copyright © 2017 Elsevier B.V. All rights reserved.

Phase separation of self-propelled ballistic particles

NASA Astrophysics Data System (ADS)

Bruss, Isaac R.; Glotzer, Sharon C.

2018-04-01

Self-propelled particles phase-separate into coexisting dense and dilute regions above a critical density. The statistical nature of their stochastic motion lends itself to various theories that predict the onset of phase separation. However, these theories are ill-equipped to describe such behavior when noise becomes negligible. To overcome this limitation, we present a predictive model that relies on two density-dependent timescales: τF, the mean time particles spend between collisions; and τC, the mean lifetime of a collision. We show that only when τF<τC do collisions last long enough to develop a growing cluster and initiate phase separation. Using both analytical calculations and active particle simulations, we measure these timescales and determine the critical density for phase separation in both two and three dimensions.

Temperature-Induced Phase Separation in Molecular Assembly of Nanotubes Comprising Amphiphilic Polypeptide with Poly( N-Ethyl Glycine) in Water by a Hydrophilic-Region Driven Type Mechanism.

PubMed

Hattori, Tetsuya; Itagaki, Toru; Uji, Hirotaka; Kimura, Shunsaku

2018-06-20

Two kinds of amphiphilic polypeptides having different types of hydrophilic polypeptoids, poly(sarcosine)-b-(L-Leu-Aib)6 (ML12) and poly(N-ethyl glycine)-b-(L-Leu-Aib)6 (EL12), were self-assembled via two paths to phase-separated nanotubes. One path was via sticking ML12 nanotubes with EL12 nanotubes, and the other was a preparation from a mixture of ML12 and EL12 in solution. In either case, nanotubes showed temperature-induced phase separation along the long axis, which was observed by two methods of labeling one phase with gold nanoparticles and fluorescence resonance energy transfer between the components. The phase-separation was ascribed to aggregation of poly(N-ethyl glycine) blocks over the cloud point temperature. The addition of 5% trifluoroethanol was needed for the phase separation, because the tight association of the helices in the hydrophobic region should be loosened to allow lateral diffusion of the components to be separated. The phase-separation in molecular assemblies in water based on the hydrophilic-region driven type mechanism therefore requires sophisticated balances of association forces exerting among the hydrophilic and hydrophobic regions of the amphiphilic polypeptoids.

Impinging jet separators for liquid metal magnetohydrodynamic power cycles

NASA Technical Reports Server (NTRS)

Bogdanoff, D. W.

1973-01-01

In many liquid metal MHD power, cycles, it is necessary to separate the phases of a high-speed liquid-gas flow. The usual method is to impinge the jet at a glancing angle against a solid surface. These surface separators achieve good separation of the two phases at a cost of a large velocity loss due to friction at the separator surface. This report deals with attempts to greatly reduce the friction loss by impinging two jets against each other. In the crude impinging jet separators tested to date, friction losses were greatly reduced, but the separation of the two phases was found to be much poorer than that achievable with surface separators. Analyses are presented which show many lines of attack (mainly changes in separator geometry) which should yield much better separation for impinging jet separators).

Variation in pH of Model Secondary Organic Aerosol during Liquid-Liquid Phase Separation.

PubMed

Dallemagne, Magda A; Huang, Xiau Ya; Eddingsaas, Nathan C

2016-05-12

The majority of atmospheric aerosols consist of both organic and inorganic components. At intermediate relative humidity (RH), atmospheric aerosol can undergo liquid-liquid phase separation (LLPS) in which the organic and inorganic fractions segregate from each other. We have extended the study of LLPS to the effect that phase separation has on the pH of the overall aerosols and the pH of the individual phases. Using confocal microscopy and pH sensitive dyes, the pH of internally mixed model aerosols consisting of polyethylene glycol 400 and ammonium sulfate as well as the pH of the organic fraction during LLPS have been directly measured. During LLPS, the pH of the organic fraction was observed to increase to 4.2 ± 0.2 from 3.8 ± 0.1 under high RH when the aerosol was internally mixed. In addition, the high spatial resolution of the confocal microscope allowed us to characterize the composition of each of the phases, and we have observed that during LLPS the organic shell still contains large quantities of water and should be characterized as an aqueous organic-rich phase rather than simply an organic phase.

Improving Reliability of a Residency Interview Process

PubMed Central

Serres, Michelle L.; Gundrum, Todd E.

2013-01-01

Objective. To improve the reliability and discrimination of a pharmacy resident interview evaluation form, and thereby improve the reliability of the interview process. Methods. In phase 1 of the study, authors used a Many-Facet Rasch Measurement model to optimize an existing evaluation form for reliability and discrimination. In phase 2, interviewer pairs used the modified evaluation form within 4 separate interview stations. In phase 3, 8 interviewers individually-evaluated each candidate in one-on-one interviews. Results. In phase 1, the evaluation form had a reliability of 0.98 with person separation of 6.56; reproducibly, the form separated applicants into 6 distinct groups. Using that form in phase 2 and 3, our largest variation source was candidates, while content specificity was the next largest variation source. The phase 2 g-coefficient was 0.787, while confirmatory phase 3 was 0.922. Process reliability improved with more stations despite fewer interviewers per station—impact of content specificity was greatly reduced with more interview stations. Conclusion. A more reliable, discriminating evaluation form was developed to evaluate candidates during resident interviews, and a process was designed that reduced the impact from content specificity. PMID:24159209

Cell Partition in Two Polymer Aqueous Phases

NASA Technical Reports Server (NTRS)

Brooks, D. E.

1985-01-01

In a reduced gravity environment the two polymer phases will not separate via density driven settling in an acceptably short length of time. It is to be expected that a certain amount of phase separation will take place, however, driven by the reduction in free energy gained when the interfacial area is reduced. This stage of separation process will therefore depend directly on the magnitude of the interfacial tension between the phases. In order to induce complete phase separation in a short time, electric field-induced separation which occurs because the droplets of one phase in the other have high electrophoretic mobilities which increase with droplet size was investigated. These mobilities are significant only in the presence of certain salts, particularly phosphates. The presence of such salts, in turn has a strong effect on the cell partition behavior in dextran-poly (ethylene glycol) (PEG) systems. The addition of the salts necessary to produce phase drop mobilities has a large effect on the interfacial tensions in the systems.

Analytical and semipreparative chiral separation of cis-itraconazole on cellulose stationary phases by high-performance liquid chromatography.

PubMed

Kurka, Ondřej; Kučera, Lukáš; Bednář, Petr

2016-07-01

cis-Itraconazole is a chiral antifungal drug administered as a racemate. The knowledge of properties of individual cis-itraconazole stereoisomers is vital information for medicine and biosciences as different stereoisomers of cis-itraconazole may possess different affinity to certain biological pathways in the human body. For this purpose, either chiral synthesis of enantiomers or chiral separation of racemate can be used. This paper presents a two-step high-performance liquid chromatography approach for the semipreparative isolation of four stereoisomers (two enantiomeric pairs) of itraconazole using polysaccharide stationary phases and volatile organic mobile phases without additives in isocratic mode. The approach used involves the separation of the racemate into three fractions (i.e. two pure stereoisomers and one mixed fraction containing the remaining two stereoisomers) in the first run and consequent separation of the collected mixed fraction in the second one. For this purpose, combination of cellulose tris-(4-methylbenzoate) and cellulose tris-(3,5-dimehylphenylcarbamate) columns with complementary selectivity for cis-itraconazole provided full separation of all four stereoisomers (with purity of each isomer > 97%). The stereoisomers were collected, their optical rotation determined and their identity confirmed based on the results of a previously published study. Pure separated stereoisomers are subjected to further biological studies. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Comparing monolithic and fused core HPLC columns for fast chromatographic analysis of fat-soluble vitamins.

PubMed

Kurdi, Said El; Muaileq, Dina Abu; Alhazmi, Hassan A; Bratty, Mohammed Al; Deeb, Sami El

2017-06-27

HPLC stationary phases of monolithic and fused core type can be used to achieve fast chromatographic separation as an alternative to UPLC. In this study, monolithic and fused core stationary phases are compared for fast separation of four fat-soluble vitamins. Three new methods on the first and second generation monolithic silica RP-18e columns and a fused core pentafluoro-phenyl propyl column were developed. Application of three fused core columns offered comparable separations of retinyl palmitate, DL-α-tocopheryl acetate, cholecalciferol and menadione in terms of elution speed and separation efficiency. Separation was achieved in approx. 5 min with good resolution (Rs > 5) and precision (RSD ≤ 0.6 %). Monolithic columns showed, however, a higher number of theoretical plates, better precision and lower column backpressure than the fused core column. The three developed methods were successfully applied to separate and quantitate fat-soluble vitamins in commercial products.

Gas-Liquid Flows and Phase Separation

NASA Technical Reports Server (NTRS)

McQuillen, John

2004-01-01

Common issues for space system designers include:Ability to Verify Performance in Normal Gravity prior to Deployment; System Stability; Phase Accumulation & Shedding; Phase Separation; Flow Distribution through Tees & Manifolds Boiling Crisis; Heat Transfer Coefficient; and Pressure Drop.The report concludes:Guidance similar to "A design that operates in a single phase is less complex than a design that has two-phase flow" is not always true considering the amount of effort spent on pressurizing, subcooling and phase separators to ensure single phase operation. While there is still much to learn about two-phase flow in reduced gravity, we have a good start. Focus now needs to be directed more towards system level problems .

High-performance liquid chromatography study of the enantiomer separation of chrysanthemic acid and its analogous compounds on a terguride-based stationary phase.

PubMed

Dondi, M; Flieger, M; Olsovska, J; Polcaro, C M; Sinibaldi, M

1999-10-29

The direct enantioseparation of chrysanthemic acid [2,2-dimethyl-3-(2-methylpropenyl)-cyclopropanecarboxylic acid] and its halogen-substituted analogues was systematically studied by HPLC using a terguride-based chiral stationary phase in combination with a UV diode array and chiroptical detectors. Isomers with (1R) configuration always eluted before those with (IS) configuration. The elution sequence of cis- and trans-isomers was strongly affected by mobile phase pH, whereas the enantioselectivity remained the same. Conditions for the separation of all the enantiomers were also examined. This method was used for monitor the hydrolytic degradation products of Cyfluthrin (Baythroid) in soil under laboratory conditions.

Dynamical phase separation using a microfluidic device: experiments and modeling

NASA Astrophysics Data System (ADS)

Aymard, Benjamin; Vaes, Urbain; Radhakrishnan, Anand; Pradas, Marc; Gavriilidis, Asterios; Kalliadasis, Serafim; Complex Multiscale Systems Team

2017-11-01

We study the dynamical phase separation of a binary fluid by a microfluidic device both from the experimental and from the modeling points of view. The experimental device consists of a main channel (600 μm wide) leading into an array of 276 trapezoidal capillaries of 5 μm width arranged on both sides and separating the lateral channels from the main channel. Due to geometrical effects as well as wetting properties of the substrate, and under well chosen pressure boundary conditions, a multiphase flow introduced into the main channel gets separated at the capillaries. Understanding this dynamics via modeling and numerical simulation is a crucial step in designing future efficient micro-separators. We propose a diffuse-interface model, based on the classical Cahn-Hilliard-Navier-Stokes system, with a new nonlinear mobility and new wetting boundary conditions. We also propose a novel numerical method using a finite-element approach, together with an adaptive mesh refinement strategy. The complex geometry is captured using the same computer-aided design files as the ones adopted in the fabrication of the actual device. Numerical simulations reveal a very good qualitative agreement between model and experiments, demonstrating also a clear separation of phases.

Liquid-liquid phase separation of freely falling undercooled ternary Fe-Cu-Sn alloy

NASA Astrophysics Data System (ADS)

Wang, W. L.; Wu, Y. H.; Li, L. H.; Zhai, W.; Zhang, X. M.; Wei, B.

2015-11-01

The active modulation and control of the liquid phase separation for high-temperature metallic systems are still challenging the development of advanced immiscible alloys. Here we present an attempt to manipulate the dynamic process of liquid-liquid phase separation for ternary Fe47.5Cu47.5Sn5 alloy. It was firstly dispersed into numerous droplets with 66 ~ 810 μm diameters and then highly undercooled and rapidly solidified under the containerless microgravity condition inside drop tube. 3-D phase field simulation was performed to explore the kinetic evolution of liquid phase separation. Through regulating the combined effects of undercooling level, phase separation time and Marangoni migration, three types of separation patterns were yielded: monotectic cell, core shell and dispersive structures. The two-layer core-shell morphology proved to be the most stable separation configuration owing to its lowest chemical potential. Whereas the monotectic cell and dispersive microstructures were both thermodynamically metastable transition states because of their highly active energy. The Sn solute partition profiles of Fe-rich core and Cu-rich shell in core-shell structures varied only slightly with cooling rate.

Large Area Crop Inventory Experiment (LACIE). Phase 3 direct wheat study of North Dakota

NASA Technical Reports Server (NTRS)

Kinsler, M. C.; Nichols, J. D.; Ona, A. L. (Principal Investigator)

1979-01-01

The author has identified the following significant results. The green number and brightness scatter plots, channel plots of radiance values, and visual study of the imagery indicate separability between barley and spring wheat/oats during the wheat mid-heading to mid-ripe stages. In the LACIE Phase 3 North Dakota data set, the separation time is more specifically the wheat soft dough stage. At this time, the barley is ripening, and is therefore, less green and brighter than the wheat. Only 4 of the 18 segments studied indicate separation of barley/other spring small grain, even though 11 of the segments have acquisitions covering the wheat soft dough stage. The remaining seven segments had less than 5 percent barley based on ground truth data.

Characterization of free thiol variants of an IgG1 by reversed phase ultra high pressure liquid chromatography coupled with mass spectrometry.

PubMed

Liu, Hongbin; Jeong, Justin; Kao, Yung-Hsiang; Zhang, Yonghua Taylor

2015-05-10

RP-HPLC has been demonstrated as a powerful tool to study antibody free thiol and disulfide variants. Recently, the introduction of UHPLC columns with wide pore size (300Å) and small particle size (1.7μm) offered the opportunity to further improve the separation of such variants. This paper describes a systematic evaluation of stationary phases, operating parameters, and mobile phases for a UHPLC based method to separate free thiol variants of a recombinant monoclonal antibody (referred as mAb A), targeting high resolution, high throughput and improved recovery. Among the four different stationary phases evaluated, UHPLC diphenyl columns were found to provide the best separation. Using an optimized UHPLC method, free thiol variants of mAb A were separated in 5min. Importantly, the UHPLC method revealed minor variants that had coeluted in an HPLC based method, and the UHPLC method is also applicable as a platform method for characterization of other mAbs as well. Furthermore, an on-line UHPLC-MS method was developed to characterize the separated variants, and this method can streamline the characterization of fully assembled monoclonal and bispecific therapeutic antibodies. Copyright © 2015 Elsevier B.V. All rights reserved.

Nanoscopy of Phase Separation in InxGa1-xN Alloys.

PubMed

Abate, Yohannes; Seidlitz, Daniel; Fali, Alireza; Gamage, Sampath; Babicheva, Viktoriia; Yakovlev, Vladislav S; Stockman, Mark I; Collazo, Ramon; Alden, Dorian; Dietz, Nikolaus

2016-09-07

Phase separations in ternary/multinary semiconductor alloys is a major challenge that limits optical and electronic internal device efficiency. We have found ubiquitous local phase separation in In1-xGaxN alloys that persists to nanoscale spatial extent by employing high-resolution nanoimaging technique. We lithographically patterned InN/sapphire substrates with nanolayers of In1-xGaxN down to few atomic layers thick that enabled us to calibrate the near-field infrared response of the semiconductor nanolayers as a function of composition and thickness. We also developed an advanced theoretical approach that considers the full geometry of the probe tip and all the sample and substrate layers. Combining experiment and theory, we identified and quantified phase separation in epitaxially grown individual nanoalloys. We found that the scale of the phase separation varies widely from particle to particle ranging from all Ga- to all In-rich regions and covering everything in between. We have found that between 20 and 25% of particles show some level of Ga-rich phase separation over the entire sample region, which is in qualitative agreement with the known phase diagram of In1-xGaxN system.

Selective determination of heavy metals (Cd, Pb, Cr) speciation forms from hortic anthrosols

NASA Astrophysics Data System (ADS)

Bulgariu, Dumitru; Bulgariu, Laura; Filipov, Feodor; Astefanei, Dan; Stoleru, Vasile

2010-05-01

In soils from glass houses, the speciation and inter-phases distribution processes of heavy metals have a particular dynamic, different in comparison with those from non-protected soils. The predominant distribution forms of heavy metals in such soils types are: complexes with low mass organic molecules, organic-mineral complexes, complexes with inorganic ligands (hydroxide-complexes, carbonate-complexes, sulphate-complexes, etc.) and basic salts. All of these have high stabilities in conditions of soils from glass houses, and in consequence, the separation and determination of speciation forms (which is directly connected with biodisponibility of heavy metals) by usual methods id very difficult and has a high uncertain degree. In this study is presented an original method for the selective separation and differentiation of speciation forms of heavy metals from glass houses soils, which is based by the combination of solid-liquid sequential extraction (SPE) with the extraction in aqueous polymer-inorganic salt two-phase systems (ABS). The soil samples used for this study have been sampled from three different locations (glass houses from Iasi, Barlad and Bacau - Romania) where the vegetables cultivation have been performed by three different technologies. In this way was estimated the applicability and the analytical limits of method proposed by as, in function of the chemical-mineralogical and physical-chemical characteristics of soils. As heavy metals have been studied cadmium, lead and chromium, all being known for their high toxicity. The procedure used for the selective separation and differentiation of speciation forms of heavy metals from glass houses soils has two main steps: (i) non-destructive separation of chemical-mineralogical associations and aggregates from soils samples - for this the separation method with heavy liquids (bromophorme) and isodynamic magnetic method have been used; (ii) sequential extraction of heavy metals from soil fractions separated in the first step, by using combined SPE-ABS procedure. For the preparation of combined extraction systems was used polyethylene glycol (with different molecular mass: 2000, 4000 and 8000). As phase-forming inorganic salts and as selective extracting agents we have used different usual inorganic reagents. The type and concentration of phase-forming salts have been selected in function of, both nature of extracted heavy metals and chemical-mineralogical characteristics of soil samples. The experimental parameters investigated in this study are: molecular mass of polyethylene glycol and the concentration of polymeric solutions, nature and concentration of phase-forming salts, nature and concentration of extracting agents, pH in extraction system phase, type of extracted heavy metals, type of speciation forms of heavy metals and their concentrations. All these factors can influence significantly the efficiency and the selectivity of separation process. The experimental results have indicate that the combined SPE-ABS extraction systems have better separation efficiency, in comparison with traditional SPE systems and ca realized a accurate discrimination between speciation forms of heavy metals from soils. Under these conditions, the estimation of inter-phases distribution and biodisponibility of heavy metals has a high precision. On the other hand, when the combined SPE-ABS systems are used, the concomitant extraction of the elements from the same geochemical association with studied heavy metals (inevitable phenomena in case of separation by SPE procedures) is significant diminished. This increases the separation selectivity and facilitated the more accurate determination of speciation forms concentration. By adequate selection of extraction conditions can be realized the selective separation of organic-mineral complexes, which will permit to perform detailed studies about the structure and chemical composition of these. Acknowledgments The authors would like to acknowledge the financial support from Romanian Ministry of Education and Research (Project PNCDI 2-D5 no. 51045/07 and project PNCDI 2 - D5 no. 52-141 / 2008).

Low density microcellular foams

DOEpatents

Aubert, J.H.; Clough, R.L.; Curro, J.G.; Quintana, C.A.; Russick, E.M.; Shaw, M.T.

1985-10-02

Low density, microporous polymer foams are provided by a process which comprises forming a solution of polymer and a suitable solvent followed by rapid cooling of the solution to form a phase-separated system and freeze the phase-separated system. The phase-separated system comprises a polymer phase and a solvent phase, each of which is substantially continuous within the other. The morphology of the polymer phase prior to and subsequent to freezing determine the morphology of the resultant foam. Both isotropic and anisotropic foams can be produced. If isotropic foams are produced, the polymer and solvent are tailored such that the solution spontaneously phase-separates prior to the point at which any component freezes. The morphology of the resultant polymer phase determines the morphology of the reusltant foam and the morphology of the polymer phase is retained by cooling the system at a rate sufficient to freeze one or both components of the system before a change in morphology can occur. Anisotropic foams are produced by forming a solution of polymer and solvent that will not phase separate prior to freezing of one or both components of the solution. In such a process, the solvent typically freezes before phase separation occurs. The morphology of the resultant frozen two-phase system determines the morphology of the resultant foam. The process involves subjecting the solution to essentially one-dimensional cooling. Foams having a density of less than 0.1 g/cc and a uniform cell size of less than 10 ..mu..m and a volume such that the foams have a length greater than 1 cm are provided.

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.

Solidification phenomena of binary organic mixtures

NASA Technical Reports Server (NTRS)

Chang, K.

1982-01-01

The coalescence rates and motion of liquid bubbles in binary organic mixtures were studied. Several factors such as temperature gradient, composition gradient, interfacial tension, and densities of the two phases play important roles in separation of phases of immiscible liquids. An attempt was made to study the effect of initial compositions on separation rates of well-dispersed organic mixtures at different temperatures and, ultimately, on the homogeneity of solidification of the immiscible binary organic liquids. These organic mixtures serve as models for metallic pseudo binary systems under study. Two specific systems were investigated: ethyl salicylate - diethyl glycol and succinonitrile - water.

Origin of Reversible Photoinduced Phase Separation in Hybrid Perovskites.

PubMed

Bischak, Connor G; Hetherington, Craig L; Wu, Hao; Aloni, Shaul; Ogletree, D Frank; Limmer, David T; Ginsberg, Naomi S

2017-02-08

The distinct physical properties of hybrid organic-inorganic materials can lead to unexpected nonequilibrium phenomena that are difficult to characterize due to the broad range of length and time scales involved. For instance, mixed halide hybrid perovskites are promising materials for optoelectronics, yet bulk measurements suggest the halides reversibly phase separate upon photoexcitation. By combining nanoscale imaging and multiscale modeling, we find that the nature of halide demixing in these materials is distinct from macroscopic phase separation. We propose that the localized strain induced by a single photoexcited charge interacting with the soft, ionic lattice is sufficient to promote halide phase separation and nucleate a light-stabilized, low-bandgap, ∼8 nm iodide-rich cluster. The limited extent of this polaron is essential to promote demixing because by contrast bulk strain would simply be relaxed. Photoinduced phase separation is therefore a consequence of the unique electromechanical properties of this hybrid class of materials. Exploiting photoinduced phase separation and other nonequilibrium phenomena in hybrid materials more generally could expand applications in sensing, switching, memory, and energy storage.

Alpha phase precipitation from phase-separated beta phase in a model Ti-Mo-Al alloy studied by direct coupling of transmission electron microscopy and atom probe tomography

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

Devaraj, Arun; Nag, Soumya; Banerjee, Rajarshi

2013-10-19

The benefit of direct coupling of APT with TEM dark field imaging to investigate early stages of phase transformation in multicomponent alloys is demonstrated by analyzing alpha phase precipitated in a model Ti-10 at% Mo-10 at% Al alloy during annealing at 400oC. Through such a direct coupling approach a thermodynamically unexpected solute partitioning trend between beta matrix and alpha precipitate is observed in the early stages of precipitation, which is explained based on possible nucleation of alpha phase in the Ti rich (Mo and Al depleted regions) created as a result of phase separation in beta matrix. On further highermore » temperature annealing at 600oC for 1 hour, the alpha precipitates were shown to grow and get enriched in Al and further depleted in Mo reaching the thermodynamic equilibrium.« less

Solar fuels generator

DOEpatents

Lewis, Nathan S.; Spurgeon, Joshua M.

2016-10-25

The solar fuels generator includes an ionically conductive separator between a gaseous first phase and a second phase. A photoanode uses one or more components of the first phase to generate cations during operation of the solar fuels generator. A cation conduit is positioned provides a pathway along which the cations travel from the photoanode to the separator. The separator conducts the cations. A second solid cation conduit conducts the cations from the separator to a photocathode.

Topology and strong four fermion interactions in four dimensions

NASA Astrophysics Data System (ADS)

Catterall, Simon; Butt, Nouman

2018-05-01

We study massless fermions interacting through a particular four-fermion term in four dimensions. Exact symmetries prevent the generation of bilinear fermion mass terms. We determine the structure of the low-energy effective action for the auxiliary field needed to generate the four-fermion term and find it has an novel structure that admits topologically nontrivial defects with nonzero Hopf invariant. We show that fermions propagating in such a background pick up a mass without breaking symmetries. Furthermore, pairs of such defects experience a logarithmic interaction. We argue that a phase transition separates a phase where these defects proliferate from a broken phase where they are bound tightly. We conjecture that, by tuning one additional operator, the broken phase can be eliminated with a single BKT-like phase transition separating the massless from massive phases.

Separation of active laccases from Pleurotus sapidus culture supernatant using aqueous two-phase systems in centrifugal partition chromatography.

PubMed

Schwienheer, C; Prinz, A; Zeiner, T; Merz, J

2015-10-01

For the production of bio active compounds, e.g., active enzymes or antibodies, a conserved purification process with a minimum loss of active compounds is necessary. In centrifugal partition chromatography (CPC), the separation effect is based on the different distribution of the components to be separated between two immiscible liquid phases. Thereby, one liquid phase is kept stationary in chambers by a centrifugal field and the mobile phase is pumped through via connecting ducts. Aqueous two phase systems (ATPS) are known to provide benign conditions for biochemical products and seem to be promising when used in CPC for purification tasks. However, it is not known if active biochemical compounds can "survive" the conditions in a CPC where strong shear forces can occur due to the two-phasic flow under centrifugal forces. Therefore, this aspect has been faced within this study by the separation of active laccases from a fermentation broth of Pleurotus sapidus. After selecting a suitable ATPS and operating conditions, the activity yield was calculated and the preservation of the active enzymes could be observed. Therefore, CPC could be shown as potentially suitable for the purification of bio-active compounds. Copyright © 2015 Elsevier B.V. All rights reserved.

Liquid-liquid phase separation and solidification behavior of Al55Bi36Cu9 monotectic alloy with different cooling rates

NASA Astrophysics Data System (ADS)

Bo, Lin; Li, Shanshan; Wang, Lin; Wu, Di; Zuo, Min; Zhao, Degang

2018-03-01

The cooling rate has a significant effect on the solidification behavior and microstructure of monotectic alloy. In this study, different cooling rate was designed through casting in the copper mold with different bore diameters. The effects of different cooling rate on the solidification behavior of Al55Bi36Cu9 (at.%) immiscible alloy have been investigated. The liquid-liquid phase separation of Al55Bi36Cu9 immiscible alloy melt was investigated by resistivity test. The solidification microstructure and phase analysis of Al55Bi36Cu9 immiscible alloy were performed by the SEM and XRD, respectively. The results showed that the liquid-liquid phase separation occurred in the solidification of Al55Bi36Cu9 monotectic melt from 917 °C to 653 °C. The monotectic temperature, liquid phase separation temperature and immiscibility zone of Al55Bi36Cu9 monotectic alloy was lower than those of Al-Bi binary monotectic alloy. The solidification morphology of Al55Bi36Cu9 monotectic alloy was very sensitive to the cooling rate. The Al/Bi core-shell structure formed when Al55Bi36Cu9 melt was cast in the copper mold with a 8 mm bore diameter.

Separation by solvent extraction

DOEpatents

Holt, Jr., Charles H.

1976-04-06

17. A process for separating fission product values from uranium and plutonium values contained in an aqueous solution, comprising adding an oxidizing agent to said solution to secure uranium and plutonium in their hexavalent state; contacting said aqueous solution with a substantially water-immiscible organic solvent while agitating and maintaining the temperature at from -1.degree. to -2.degree. C. until the major part of the water present is frozen; continuously separating a solid ice phase as it is formed; separating a remaining aqueous liquid phase containing fission product values and a solvent phase containing plutonium and uranium values from each other; melting at least the last obtained part of said ice phase and adding it to said separated liquid phase; and treating the resulting liquid with a new supply of solvent whereby it is practically depleted of uranium and plutonium.

Stepwise pH-gradient elution for the preparative separation of natural anthraquinones by multiple liquid-liquid partition.

PubMed

Hynninen, P H; Räisänen, R

2001-01-01

Preparative-scale separation of substituted anthraquinones by multiple liquid-liquid partition was studied using isopropylmethyl ketone (IMK)/aqueous phosphate buffer (aq.) as the solvent system and the Hietala apparatus with 100 partition units as the partition equipment. The lower (aq.) phase was chosen as mobile, while the upper (IMK) phase remained stationary. Hence, the principle of stepwise pH-gradient elution could be utilized to separate the components in two complex mixtures of hydroxyanthraquinones and hydroxyanthraquinone carboxylic acids, isolated from the fungus Dermocybe sanguinea. In spite of the nonlinearity of the partition isotherms for these anthraquinones, implying deviations from the Nernst partition law, remarkable separations were achieved for the components in each mixture. Every anthraquinone carboxylic acid showed markedly irregular partition behavior, appearing in the effluent as two more or less resolved concentration zones. Such splitting was attributed to the formation of relatively stable sandwich-dimers, which were in a slow equilibrium with the monomers in the more nonpolar organic phase. At lower pH-values, only the polar monomers were distributed into the mobile aqueous phase and moved forward, whereas the nonpolar sandwich-dimers remained almost entirely in the stationary organic phase and lagged behind. When the pH of the mobile aqueous phase was raised high enough, the firmly linked dimers were monomerized and emerged from the apparatus as a second concentration profile. Intermolecular hydrogen bonding and pi-pi interaction between the pi-systems of two anthraquinone molecules in a parallel orientation were considered responsible for the nonlinear and markedly irregular partition behavior of the natural anthraquinones studied. The nonlinearity of the partition behavior of the hydroxyanthraquinones lacking the carboxyl group, appeared merely as excessive broadening of the experimental concentration profile, which impaired the resolution between the components only insignificantly. Thus, e.g. the main components, dermocybin and emodin, could both be obtained from Separation 1 in a purity of at least 99%.

Phase Separation in Solutions of Monoclonal Antibodies

NASA Astrophysics Data System (ADS)

Benedek, George; Wang, Ying; Lomakin, Aleksey; Latypov, Ramil

2012-02-01

We report the observation of liquid-liquid phase separation (LLPS) in a solution of humanized monoclonal antibodies, IgG2, and the effects of human serum albumin, a major blood protein, on this phase separation. We find a significant reduction of phase separation temperature in the presence of albumin, and a preferential partitioning of the albumin into the antibody-rich phase. We provide a general thermodynamic analysis of the antibody-albumin mixture phase diagram and relate its features to the magnitude of the effective inter-protein interactions. Our analysis suggests that additives (HSA in this report), which have moderate attraction with antibody molecules, may be used to forestall undesirable protein condensation in antibody solutions. Our findings are relevant to understanding the stability of pharmaceutical solutions of antibodies and the mechanisms of cryoglobulinemia.

The solubility of gallium oxide in vapor and two-phase fluid filtration in hydrothermal systems

NASA Astrophysics Data System (ADS)

Bychkov, Andrew; Matveeva, Svetlana; Nekrasov, Stanislav

2010-05-01

The solubility of gallium and aluminum oxides in gas phase in the system Ga2O3 (Al2O3)-HCl-H2O was studied at 150-350°C and pressure up to saturated vapor. The concentration of gallium increases with the increasing of HCl pressure. The formulae of gallium gaseous specie was determined as GaOHCl2. The constant of gallium oxide solubility reaction was calculated at 150, 200, 250, 300 and 350°C. The concentration of aluminum in gas phase is insignificant in the same conditions. The possibility of gallium transportation in gas phase with small quantity of Al allow to divide this elements in hydrothermal processes with gas phase. The Ga/Al ratio in muscovite can be used as the indicator of gas phase separation and condensation. This indicator was not considered in the geochemical literature earlier. The separation of gas and liquid phases was determined in Akchatau (Kazahstan) and Spokoinoe (Russia) greisen W deposit by carbon isotope fractionation of carbon dioxide in fluid inclusion. The important feature of both ore mains is heterogenization and boiling of ore-forming fluids. Greisen ore bodies are formed as a result of strongly focused solution flow in the T-P gradient fields. It is possible to divide ore bodies of Akchatau in two types: muscovite and quartz. Muscovite type veins are thin and have small metasyntactic zone. Quartz type veins are localized in fault with large vertical extent (500 m) and content the large quantity of wolframite. These veins formed in condition of significant pressure decreasing from 2.5 to 0.5 kbar with fluid boiling. Gas and liquid phase separation specifies the vertical zonality of quartz type veins. The gas phase with the high gallium concentration is separated from a flow of liquid phase. Liquid phase react with the granites forming greisen metasomatites. Condensation of the gas phase in upper parts of massive produces the increasing of Ga/Al ratio in muscovite 3-5 times more, then in granites and bottom part of vein (from 2×10-4 to 8×10-4 mass ratio). The muscovite type veins has no separation between gas and liquid due to there thickness and small pressure gradient. There is no difference in Ga/Al ratio in muscovite from this veins. The Spokoinoe deposit is classified by mineralized dome type. The heterogenization of fluid occurs in H2O-CO2 system for water phase and carbon dioxide with temperature decreasing. Two-phase flow is separated in granite, forming greisen metosomatites. The Ga/Al ratio in rock increase up to 3 times to the upper part of metasomatitic zone. The Ga/Al ratio in muscovite can be applied for other hydrothermal systems for geochemical indicator of gas phase separation and condensation zone determination. This work is supported by RFBR project 10-05-00670 and 10-05-00320.

Scattering Studies of Hydrophobic Monomers in Liposomal Bilayers: An Expanding Shell Model of Monomer Distribution

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

Richter, Andrew; Dergunov, Sergey; Ganus, Bill

2011-01-01

Hydrophobic monomers partially phase separate from saturated lipids when loaded into lipid bilayers in amounts exceeding a 1:1 monomer/lipid molar ratio. This conclusion is based on the agreement between two independent methods of examining the structure of monomer-loaded bilayers. Complete phase separation of monomers from lipids would result in an increase in bilayer thickness and a slight increase in the diameter of liposomes. A homogeneous distribution of monomers within the bilayer would not change the bilayer thickness and would lead to an increase in the liposome diameter. The increase in bilayer thickness, measured by the combination of small-angle neutron scatteringmore » (SANS) and small-angle X-ray scattering (SAXS), was approximately half of what was predicted for complete phase separation. The increase in liposome diameter, measured by dynamic light scattering (DLS), was intermediate between values predicted for a homogeneous distribution and complete phase separation. Combined SANS, SAXS, and DLS data suggest that at a 1.2 monomer/lipid ratio approximately half of the monomers are located in an interstitial layer sandwiched between lipid sheets. These results expand our understanding of using self-assembled bilayers as scaffolds for the directed covalent assembly of organic nanomaterials. In particular, the partial phase separation of monomers from lipids corroborates the successful creation of nanothin polymer materials with uniform imprinted nanopores. Pore-forming templates do not need to span the lipid bilayer to create a pore in the bilayer-templated films.« less

Scattering Studies of Hydrophobic Monomers in Liposomal Bilayers: An Expanding Shell Model of Monomer Distribution

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

Richter, Andrew G.; Dergunov, Sergey A.; Ganus, Bill

2011-03-10

Hydrophobic monomers partially phase separate from saturated lipids when loaded into lipid bilayers in amounts exceeding a 1:1 monomer/lipid molar ratio. This conclusion is based on the agreement between two independent methods of examining the structure of monomer-loaded bilayers. Complete phase separation of monomers from lipids would result in an increase in bilayer thickness and a slight increase in the diameter of liposomes. A homogeneous distribution of monomers within the bilayer would not change the bilayer thickness and would lead to an increase in the liposome diameter. The increase in bilayer thickness, measured by the combination of small-angle neutron scatteringmore » (SANS) and small-angle X-ray scattering (SAXS), was approximately half of what was predicted for complete phase separation. The increase in liposome diameter, measured by dynamic light scattering (DLS), was intermediate between values predicted for a homogeneous distribution and complete phase separation. Combined SANS, SAXS, and DLS data suggest that at a 1.2 monomer/lipid ratio approximately half of the monomers are located in an interstitial layer sandwiched between lipid sheets. These results expand our understanding of using self-assembled bilayers as scaffolds for the directed covalent assembly of organic nanomaterials. In particular, the partial phase separation of monomers from lipids corroborates the successful creation of nanothin polymer materials with uniform imprinted nanopores. Finally, pore-forming templates do not need to span the lipid bilayer to create a pore in the bilayer-templated films.« less

Improved Separations of Proteins and Sugar Derivatives Using the Small-Scale Cross-Axis Coil Planet Centrifuge with Locular Multilayer Coiled Columns

PubMed Central

Shinomiya, Kazufusa; Umezawa, Motoki; Seki, Manami; Nitta, Jun; Zaima, Kazumasa; Harikai, Naoki; Ito, Yoichiro

2016-01-01

1) Background Countercurrent chromatography (CCC) is liquid-liquid partition chromatography without using a solid support matrix. This technique requires further improvement of partition efficiency and shortening theseparation time. 2) Methods The locular multilayer coils modified with and without mixer glass beads were developed for the separation of proteins and 4-methylumbelliferyl (MU) sugar derivatives using the small-scale cross-axis coil planet centrifuge. 3) Results Proteins were well separated from each other and the separation was improved at a low flow rate of the mobile phase. On the other hand, 4-MU sugar derivatives were sufficiently resolved with short separation time at a highflow rate of the mobile phase under satisfactory stationary phase retention. 4) Conclusion Effective separations were achieved using the locular multilayer coil for proteins with aqueous-aqueous polymer phase systems and for 4-MU sugar derivatives with organic-aqueous two-phase solvent systems by inserting a glass bead into each locule. PMID:27891507

The Role of RNA in Biological Phase Separations.

PubMed

Fay, Marta M; Anderson, Paul J

2018-05-10

Phase transitions that alter the physical state of ribonucleoprotein particles contribute to the spacial and temporal organization of the densely packed intracellular environment. This allows cells to organize biologically coupled processes as well as respond to environmental stimuli. RNA plays a key role in phase separation events that modulate various aspects of RNA metabolism. Here, we review the role that RNA plays in ribonucleoprotein phase separations. Copyright © 2018 Elsevier Ltd. All rights reserved.

Phase behavior of casein micelles/exocellular polysaccharide mixtures: Experiment and theory

NASA Astrophysics Data System (ADS)

Tuinier, R.; de Kruif, C. G.

1999-05-01

Dispersions of casein micelles and an exocellular polysaccharide (EPS), obtained from Lactococcus lactis subsp. cremoris NIZO B40 EPS, show a phase separation. The phase separation is of the colloidal gas-liquid type. We have determined a phase diagram that describes the separation of skim milk with EPS into a casein-micelle rich phase and an EPS rich phase. We compare the phase diagram with those calculated from theories developed by Vrij, and by Lekkerkerker and co-workers, showing that the experimental phase boundary can be predicted quite well. From dynamic light scattering measurements of the self-diffusion of the casein micelles in the presence of EPS the spinodal could be located and it corresponds with the experimental phase boundary.

Quantum phase transition and protected ideal transport in a Kondo chain

DOE PAGES

Tsvelik, A. M.; Yevtushenko, O. M.

2015-11-30

We study the low energy physics of a Kondo chain where electrons from a one-dimensional band interact with magnetic moments via an anisotropic exchange interaction. It is demonstrated that the anisotropy gives rise to two different phases which are separated by a quantum phase transition. In the phase with easy plane anisotropy, Z2 symmetry between sectors with different helicity of the electrons is broken. As a result, localization effects are suppressed and the dc transport acquires (partial) symmetry protection. This effect is similar to the protection of the edge transport in time-reversal invariant topological insulators. The phase with easy axismore » anisotropy corresponds to the Tomonaga-Luttinger liquid with a pronounced spin-charge separation. The slow charge density wave modes have no protection against localizatioin.« less

Studies on aqueous two phase polymer systems useful for partitioning of biological materials

NASA Technical Reports Server (NTRS)

Brooks, D. E.; Bamberger, S.

1982-01-01

The two phase systems that result when aqueous solutions of dextran and poly(ethylene glycol) (PEG) are mixed above a critical concentration of a few percent provide a useful medium for the separation of biological cell subpopulations via partition between the top, PEG-rich phase and the liquid-liquid phase boundary. Interfacial tensions of such systems have been measured by the rotating drop technique and found to range between 0.1-100 micro-N/m. The tension was found to depend on the length of the tie line describing the system on a phase diagram, via a power law relationship which differed depending on the concentration of Na phosphate buffer present. The electrokinetic properties of drops of one phase suspended in the other were studied for a variety of systems. It was found that the droplet electrophoretic mobility increased monotonically with phosphate concentration and drop diameter but exhibited the opposite sign from that anticipated from phosphate partition measurements. It was possible to take advantage of these electrokinetic properties and dramatically enhance the speed of phase separation through application of relatively small electric fields.

Phenomenological model and phase behavior of saturated and unsaturated lipids and cholesterol.

PubMed

Putzel, G Garbès; Schick, M

2008-11-15

We present a phenomenological theory for the phase behavior of ternary mixtures of cholesterol and saturated and unsaturated lipids, one that describes both liquid and gel phases. It leads to the following description of the mechanism of the phase behavior: In a binary system of the lipids, phase separation occurs when the saturated chains are well ordered, as in the gel phase, simply due to packing effects. In the liquid phase, the saturated ones are not sufficiently well ordered for separation to occur. The addition of cholesterol, however, increases the saturated lipid order to the point that phase separation is once again favorable. Our theory addresses this last mechanism-the means by which cholesterol-mediated ordering of membrane lipids leads to liquid-liquid immiscibility. It produces, for the system above the main chain transition of the saturated lipid, phase diagrams in which there can be liquid-liquid phase separation in the ternary system but not in any of the binary ones, while below that temperature it yields the more common phase diagram in which a gel phase, rich in saturated lipid, appears in addition to the two liquid phases.

Separation of gas from liquid in a two-phase flow system

NASA Technical Reports Server (NTRS)

Hayes, L. G.; Elliott, D. G.

1973-01-01

Separation system causes jets which leave two-phase nozzles to impinge on each other, so that liquid from jets tends to coalesce in center of combined jet streams while gas phase is forced to outer periphery. Thus, because liquid coalescence is achieved without resort to separation with solid surfaces, cycle efficiency is improved.

Atomic Force Microscopy Studies of Functional and Dysfunctional Pulmonary Surfactant Films. I. Micro- and Nanostructures of Functional Pulmonary Surfactant Films and the Effect of SP-A

PubMed Central

Zuo, Yi Y.; Keating, Eleonora; Zhao, Lin; Tadayyon, Seyed M.; Veldhuizen, Ruud A. W.; Petersen, Nils O.; Possmayer, Fred

2008-01-01

Monolayers of a functional pulmonary surfactant (PS) can reach very low surface tensions well below their equilibrium value. The mechanism by which PS monolayers reach such low surface tensions and maintain film stability remains unknown. As shown previously by fluorescence microscopy, phospholipid phase transition and separation seem to be important for the normal biophysical properties of PS. This work studied phospholipid phase transitions and separations in monolayers of bovine lipid extract surfactant using atomic force microscopy. Atomic force microscopy showed phospholipid phase separation on film compression and a monolayer-to-multilayer transition at surface pressure 40–50 mN/m. The tilted-condensed phase consisted of domains not only on the micrometer scale, as detected previously by fluorescence microscopy, but also on the nanometer scale, which is below the resolution limits of conventional optical methods. The nanodomains were embedded uniformly within the liquid-expanded phase. On compression, the microdomains broke up into nanodomains, thereby appearing to contribute to tilted-condensed and liquid-expanded phase remixing. Addition of surfactant protein A altered primarily the nanodomains and promoted the formation of multilayers. We conclude that the nanodomains play a predominant role in affecting the biophysical properties of PS monolayers and the monolayer-to-multilayer transition. PMID:18212010

Retention behavior of long chain quaternary ammonium homologues and related nitroso-alkymethylamines

USGS Publications Warehouse

Abidi, S.L.

1985-01-01

Several chromatographic methods have been utilized to study the retentionbehavior of a homologous series of n-alkylbenzyldimethylammonium chlorides (ABDAC) and the corresponding nitroso-n-alkylmethylamines (NAMA). Linear correlation of the logarithmic capacity factor (k') with the number of carbons in the alkyl chain provides useful information on both gas chromatographic (GC) and high-performance liquid chromatographich (HPLC) retention parameters of unknown components. Under all conditions empolyed, GC methodology has proved effective in achieving complete resolution of the homologous mixture of NMA despite its obvious inadequacy in the separation of E-Z configurational isomers. Conversely, normal-phase HPLC on silica demonstrates that the selectivity (a) value for an E-Z pair is much higher than that for an adjacent homologous pair. In the reversed-phase HPLC study, three different silica-based column systems were examined under various mobile phase conditions. The extent of variation in k' was found to be a function of the organic modifier, counter-ion concentration, eluent pH, nature of counter-ion, and the polarity and type of stationary phase. The k'—[NaClO4] profiles showed similar trends between the ABDAC and the NAMA series, supporting the dipolar electronic structures of the latter compounds. Mobile phase and stationary phase effects on component separation are described. The methodology presented establishes the utility of HPLC separation techniques as versatile analytical tools for practical application.

Cell separations and the demixing of aqueous two phase polymer solutions in microgravity

NASA Technical Reports Server (NTRS)

Brooks, Donald E.; Bamberger, Stephan; Harris, J. M.; Van Alstine, James M.

1991-01-01

Partition in phase separated aqueous polymer solutions is a cell separation procedure thought to be adversely influenced by gravity. In preparation for performing cell partitioning experiments in space, and to provide general information concerning the demixing of immiscible liquids in low gravity, a series of phase separated aqueous polymer solutions have been flown on two shuttle flights. Fluorocarbon oil and water emulsions were also flown on the second flight. The aqueous polymer emulsions, which in one g demix largely by sedimentation and convection due to the density differences between the phases, demixed more slowly than on the ground and the final disposition of the phases was determined by the wetting of the container wall by the phases. The demixing behavior and kinetics were influenced by the phase volume ratio, physical properties of the systems and chamber wall interaction. The average domain size increased linearly with time as the systems demixed.

Preparative isolation of flavonoid glycosides from Sphaerophysa salsula using hydrophilic interaction solid-phase extraction coupled with two-dimensional preparative liquid chromatography.

PubMed

Jiao, Lijin; Tao, Yanduo; Wang, Weidong; Shao, Yun; Mei, Lijuan; Wang, Qilan; Dang, Jun

2017-10-01

An offline preparative two-dimensional reversed-phase liquid chromatography/hydrophilic interaction liquid chromatography coupled with hydrophilic interaction solid-phase extraction method was developed for the preparative isolation of flavonoid glycosides from a crude sample of Sphaerophysa salsula. First, the non-flavonoids were removed using an XAmide solid-phase extraction cartridge. Based on the separation results of three different chromatographic stationary phases, the first-dimensional preparation was performed on an XAqua C18 prep column, and 15 fractions were obtained from the 5.2 g target sample. Then, three representative fractions were selected for additional purification on an XAmide preparative column to further isolate the flavonoid glycosides. In all, eight flavonoid glycosides were isolated in purities over 97%. The results demonstrated that the two-dimensional liquid chromatography method used in this study was effective for the preparative separation of flavonoid glycosides from Sphaerophysa salsula. Additionally, this method showed great potential for the separation of flavonoid glycosides from other plant materials. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Rationalizing the light-induced phase separation of mixed halide organic–inorganic perovskites

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

Draguta, Sergiu; Sharia, Onise; Yoon, Seog Joon

Mixed halide hybrid perovskites, CH 3NH 3Pb(I 1-xBrx) 3' represent good candidates for lowcost, high efficiency photovoltaic, and light-emitting devices. Their band gaps can be tuned from 1.6 to 2.3 eV, by changing the halide anion identity. Unfortunately, mixed halide perovskites undergo phase separation under illumination. This leads to iodide- and bromide-rich domains along with corresponding changes to the material’s optical/electrical response. Here, using combined spectroscopic measurements and theoretical modeling, we quantitatively rationalize all microscopic processes that occur during phase separation. Our model suggests that the driving force behind phase separation is the bandgap reduction of iodiderich phases. It additionallymore » explains observed non-linear intensity dependencies, as well as self-limited growth of iodide-rich domains. Most importantly, our model reveals that mixed halide perovskites can be stabilized against phase separation by deliberately engineering carrier diffusion lengths and injected carrier densities.« less

Rationalizing the light-induced phase separation of mixed halide organic–inorganic perovskites

DOE PAGES

Draguta, Sergiu; Sharia, Onise; Yoon, Seog Joon; ...

2017-08-04

Mixed halide hybrid perovskites, CH 3NH 3Pb(I 1-xBrx) 3' represent good candidates for lowcost, high efficiency photovoltaic, and light-emitting devices. Their band gaps can be tuned from 1.6 to 2.3 eV, by changing the halide anion identity. Unfortunately, mixed halide perovskites undergo phase separation under illumination. This leads to iodide- and bromide-rich domains along with corresponding changes to the material’s optical/electrical response. Here, using combined spectroscopic measurements and theoretical modeling, we quantitatively rationalize all microscopic processes that occur during phase separation. Our model suggests that the driving force behind phase separation is the bandgap reduction of iodiderich phases. It additionallymore » explains observed non-linear intensity dependencies, as well as self-limited growth of iodide-rich domains. Most importantly, our model reveals that mixed halide perovskites can be stabilized against phase separation by deliberately engineering carrier diffusion lengths and injected carrier densities.« less

Visualization of entry flow separation for oscillating flow in tubes

NASA Technical Reports Server (NTRS)

Qiu, Songgang; Simon, Terence W.

1992-01-01

Neutrally buoyant helium-filled soap bubbles with laser illumination are used to document entry flow separation for oscillating flow in tubes. For a symmetric entry case, the size of the separation zone appears to mildly depend on Reynolds number in the acceleration phase, but is roughly Reynolds number independent in the deceleration phase. For the asymmetric entry case, the separation zone was larger and appeared to grow somewhat during the deceleration phase. The separation zones for both entry geometry cases remain relatively small throughout the cycle. This is different from what would be observed in all-laminar, oscillator flows and is probably due to the high turbulence of the flow, particularly during the deceleration phase of the cycle.

Description and Evaluation of Chiral Interactive Sites on Bonded Cyclodextrin Stationary Phases for Liquid Chromatography

NASA Astrophysics Data System (ADS)

Beesley, Thomas E.

Development of chiral separations has been essential to the drug discovery and development process. The solubility requirements for a number of methods and/or the mobile phase requirements for application of certain detection systems have opened up many opportunities for cyclodextrin-based CSPs for liquid chromatography. Even though a few chiral stationary phases cover a wide area of enantioselectivity, they do not meet the entire needs of the industry. Cyclodextrin phases offer some unique mechanisms and opportunities to resolve chiral separation problems especially in the aqueous reversed-phase and non-aqueous polar organic modes. This chapter addresses the need to understand the chiral stationary phase structure, the mechanisms at work, and the role mobile phase composition plays in driving those mechanisms to produce enantioselectivity. In addition, the development of certain derivatives has played an essential part in expanding that basic role for certain chiral separations. What these derivatives contribute in concert with the basic structure is a critical part of the understanding to the effective use of these phases. During this study it was determined that the role of steric hindrance has been vastly underestimated, both to the extent that it has occurred and to its effectiveness for obtaining enantioselectivity. References to the entire 20-year history of the cyclodextrin phase development and application literature up to this current date have been reviewed and incorporated.

[Influence of mobile phase composition on chiral separation of organic selenium racemates].

PubMed

Han, Xiao-qian; Qi, Bang-feng; Dun, Hui-juan; Zhu, Xin-yi; Na, Peng-jun; Jiang, Sheng-xiang; Chen, Li-ren

2002-05-01

The chiral separation of some chiral compounds with similar structure on the cellulose tris (3,5-dimethylphenylcarbamate) chiral stationary phase prepared by us was obtained. Ternary mobile phases influencing chiral recognition were investigated. A mode of interaction between the structural character of samples and chiral stationary phase is discussed. The results indicated that the retention and chiral separation of the analytes had a bigger change with minute addition of alcohols or acetonitrile as modifier in n-hexane/2-propanol (80/20, volume ratio) binary mobile phase.

Sensitivity of snow process simulations to precipitation-phase transition method in forested and open areas

NASA Astrophysics Data System (ADS)

Lundberg, A.; Gustafsson, D.

2009-04-01

Modeling of forest snow processes is complicated and especially problematic seems to be the separation of precipitation phase in climates where a large part of the precipitation falls at temperatures near zero degrees Celsius. When the precipitation is classified as snow, the tree crowns can carry an order of magnitude more canopy storage as compared to when the precipitation is classified as rain, and snow in the trees also alters the albedo of the forest while rain does not. Many different schemes for the precipitation phase separation are used by various snow models. Some models use just one air temperature threshold (TR/S) below which all precipitation is assumed to be snow and above which all precipitation is classified as rain. A more common approach for forest snow models is to use two temperature thresholds. The snow fraction (SF) is then set to one below the snow threshold (TS) and to zero above the rain threshold (TR) and SF is assumed to decrease linearly between these two thresholds. Also more sophisticated schemes exist, but three seems to be a lack of agreement on how the precipitation phase separations should be performed. The aim with this study is to use a hydrological model including canopy snow processes to illustrate the sensitivity for different formulations of the precipitation phase separation on a) the simulated maximum snow pack storage b) the interception evaporation loss and c) snow melt runoff. In other words, to investigate of the choice of precipitation phase separation has an impact on the simulated wintertime water balance. Simulations are made for sites in different climates and for both open fields and forest sites in different regions of Sweden from north to south. In general, precipitation phase separation methods that classified snowfall at higher temperatures resulted in a larger proportion of the precipitation lost by interception evaporation as a result of the increased interception capacity. However, the maximum snow accumulation was also increased in some cases due to the overall increased snowfall, depending on canopy density and precipitation and temperature regimes. Results show that the choice of precipitation phase separation method can have an significant impact on the simulated wintertime water balance, especially in forested regions.

Coarsening and pattern formation during true morphological phase separation in unstable thin films under gravity

NASA Astrophysics Data System (ADS)

Kumar, Avanish; Narayanam, Chaitanya; Khanna, Rajesh; Puri, Sanjay

2017-12-01

We address in detail the problem of true morphological phase separation (MPS) in three-dimensional or (2 +1 )-dimensional unstable thin liquid films (>100 nm) under the influence of gravity. The free-energy functionals of these films are asymmetric and show two points of common tangency, which facilitates the formation of two equilibrium phases. Three distinct patterns formed by relative preponderance of these phases are clearly identified in "true MPS". Asymmetricity induces two different pathways of pattern formation, viz., defect and direct pathway for true MPS. The pattern formation and phase-ordering dynamics have been studied using statistical measures such as structure factor, correlation function, and growth laws. In the late stage of coarsening, the system reaches into a scaling regime for both pathways, and the characteristic domain size follows the Lifshitz-Slyozov growth law [L (t ) ˜t1 /3] . However, for the defect pathway, there is a crossover of domain growth behavior from L (t ) ˜t1 /4→t1 /3 in the dynamical scaling regime. We also underline the analogies and differences behind the mechanisms of MPS and true MPS in thin liquid films and generic spinodal phase separation in binary mixtures.

Research on the use of space resources

NASA Technical Reports Server (NTRS)

Carroll, W. F. (Editor)

1983-01-01

The second year of a multiyear research program on the processing and use of extraterrestrial resources is covered. The research tasks included: (1) silicate processing, (2) magma electrolysis, (3) vapor phase reduction, and (4) metals separation. Concomitant studies included: (1) energy systems, (2) transportation systems, (3) utilization analysis, and (4) resource exploration missions. Emphasis in fiscal year 1982 was placed on the magma electrolysis and vapor phase reduction processes (both analytical and experimental) for separation of oxygen and metals from lunar regolith. The early experimental work on magma electrolysis resulted in gram quantities of iron (mixed metals) and the identification of significant anode, cathode, and container problems. In the vapor phase reduction tasks a detailed analysis of various process concepts led to the selection of two specific processes designated as ""Vapor Separation'' and ""Selective Ionization.'' Experimental work was deferred to fiscal year 1983. In the Silicate Processing task a thermophysical model of the casting process was developed and used to study the effect of variations in material properties on the cooling behavior of lunar basalt.

Cellulose tris-(3,5-dimethylphenylcarbamate)-based chiral stationary phase for the enantioseparation of drugs in supercritical fluid chromatography: comparison with HPLC.

PubMed

Kalíková, Květa; Martínková, Monika; Schmid, Martin G; Tesařová, Eva

2018-03-01

A cellulose tris-(3,5-dimethylphenylcarbamate)-based chiral stationary phase was studied as a tool for the enantioselective separation of 21 selected analytes with different pharmaceutical and physicochemical properties. The enantioseparations were performed using supercritical fluid chromatography. The effect of the mobile phase composition was studied. Four different additives (diethylamine, triethylamine, isopropylamine, and trifluoroacetic acid) and isopropylamine combined with trifluoroacetic acid were tested and their influence on enantioseparation was compared. The influence of two different mobile phase co-solvents (methanol and propan-2-ol) combined with all the additives was also evaluated. The best mobile phase compositions for the separation of the majority of enantiomers were CO 2 /methanol/isopropylamine 80:20:0.1 v/v/v or CO 2 /propan-2-ol/isopropylamine/trifluoroacetic acid 80:20:0.05:0.05 v/v/v/v. The best results were obtained from the group of basic β-blockers. A high-performance liquid chromatography separation system composed of the same stationary phase and mobile phase of similar properties prepared as a mixture of hexane/propan-2-ol/additive 80:20:0.1 v/v/v was considered for comparison. Supercritical fluid chromatography was found to yield better results, i.e. better enantioresolution for shorter analysis times than high-performance liquid chromatography. However, examples of enantiomers better resolved under the optimized conditions in high-performance liquid chromatography were also found. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Role of lipid phase separations and membrane hydration in phospholipid vesicle fusion.

PubMed

Hoekstra, D

1982-06-08

The relationship between lipid phase separation and fusion of small unilamellar phosphatidylserine-containing vesicles was investigated. The kinetics of phase separation were monitored by following the increase of self-quenching of the fluorescent phospholipid analogue N-(7-nitro-2,1,3-benzoxadiazol-4-yl)phosphatidylethanolamine, which occurs when the local concentration of the probe increases upon Ca2+-induced phase separation in phosphatidylserine (PS) bilayers [Hoekstra, D. (1982) Biochemistry 21, 1055-1061]. Fusion was determined by using the resonance energy transfer fusion assay [Struck, D. K., Hoekstra, D., & Pagano, R. E. (1981) Biochemistry 20, 4093-4099], which monitors the mixing of fluorescent lipid donor and acceptor molecules, resulting in an increase in energy transfer efficiency. The results show that in the presence of Ca2+, fusion proceeds much more rapidly (t 1/2 less than 5 s) than the process of phase separation (T 1/2 congruent to 1 min). Mg2+ also induced fusion, albeit at higher concentrations than Ca2+. Mg2+-induced phase separation were not detected, however. Subthreshold concentrations of Ca2+ (0.5 mM) or Mg2+ (2 mM) induced extensive fusion of PS-containing vesicles in poly(ethylene glycol) containing media. This effect did not appear to be a poly(ethylene glycol)-facilitated enhancement of cation binding to the bilayer, and consequently Ca2+-induced phase separation was not observed. The results suggest that macroscopic phase separation may facilitate but does not induced the fusion process and is therefore, not directly involved in the actual fusion mechanism. The fusion experiments performed in the presence of poly(ethylene glycol) suggest that the degree of bilayer dehydration and the creation of "point defects" in the bilayer without rigorous structural rearrangements in the membrane are dominant factors in the initial fusion events.

Simple views on critical binary liquid mixtures in porous glass

NASA Astrophysics Data System (ADS)

Tremblay, L.; Socol, S. M.; Lacelle, S.

2000-01-01

A simple scenario, different from previous attempts, is proposed to resolve the problem of the slow phase separation dynamics of binary liquid mixtures confined in porous Vycor glass. We demonstrate that simply mutual diffusion, renormalized by critical composition fluctuations and geometrical hindrance of the porous glass, accounts for the slow phase separation kinetics. Capillary invasion studies of porous Vycor glass by the critical isobutyric acid-water mixture, close to the consolute solution temperature, corroborate our analysis.

Enantioseparation of Racemic Flurbiprofen by Aqueous Two-Phase Extraction With Binary Chiral Selectors of L-dioctyl Tartrate and L-tryptophan.

PubMed

Chen, Zhi; Zhang, Wei; Wang, Liping; Fan, Huajun; Wan, Qiang; Wu, Xuehao; Tang, Xunyou; Tang, James Z

2015-09-01

A novel method for chiral separation of flurbiprofen enantiomers was developed using aqueous two-phase extraction (ATPE) coupled with biphasic recognition chiral extraction (BRCE). An aqueous two-phase system (ATPS) was used as an extracting solvent which was composed of ethanol (35.0% w/w) and ammonium sulfate (18.0% w/w). The chiral selectors in ATPS for BRCE consideration were L-dioctyl tartrate and L-tryptophan, which were screened from amino acids, β-cyclodextrin derivatives, and L-tartrate esters. Factors such as the amounts of L-dioctyl tartrate and L-tryptophan, pH, flurbiprofen concentration, and the operation temperature were investigated in terms of chiral separation of flurbiprofen enantiomers. The optimum conditions were as follows: L-dioctyl tartrate, 80 mg; L-tryptophan, 40 mg; pH, 4.0; flurbiprofen concentration, 0.10 mmol/L; and temperature, 25 °C. The maximum separation factor α for flurbiprofen enantiomers could reach 2.34. The mechanism of chiral separation of flurbiprofen enantiomers is discussed and studied. The results showed that synergistic extraction has been established by L-dioctyl tartrate and L-tryptophan, which enantioselectively recognized R- and S-enantiomers in top and bottom phases, respectively. Compared to conventional liquid-liquid extraction, ATPE coupled with BRCE possessed higher separation efficiency and enantioselectivity without the use of any other organic solvents. The proposed method is a potential and powerful alternative to conventional extraction for separation of various enantiomers. © 2015 Wiley Periodicals, Inc.

Independent active and thermodynamic processes govern the nucleolus assembly in vivo

PubMed Central

Falahati, Hanieh; Wieschaus, Eric

2017-01-01

Membraneless organelles play a central role in the organization of protoplasm by concentrating macromolecules, which allows efficient cellular processes. Recent studies have shown that, in vitro, certain components in such organelles can assemble through phase separation. Inside the cell, however, such organelles are multicomponent, with numerous intermolecular interactions that can potentially affect the demixing properties of individual components. In addition, the organelles themselves are inherently active, and it is not clear how the active, energy-consuming processes that occur constantly within such organelles affect the phase separation behavior of the constituent macromolecules. Here, we examine the phase separation model for the formation of membraneless organelles in vivo by assessing the two features that collectively distinguish it from active assembly, namely temperature dependence and reversibility. We use a microfluidic device that allows accurate and rapid manipulation of temperature and examine the quantitative dynamics by which six different nucleolar proteins assemble into the nucleoli of Drosophila melanogaster embryos. Our results indicate that, although phase separation is the main mode of recruitment for four of the studied proteins, the assembly of the other two is irreversible and enhanced at higher temperatures, behaviors indicative of active recruitment to the nucleolus. These two subsets of components differ in their requirements for ribosomal DNA; the two actively assembling components fail to assemble in the absence of ribosomal DNA, whereas the thermodynamically driven components assemble but lose temporal and spatial precision. PMID:28115706

Experimental investigation of inhomogeneities, nanoscopic phase separation, and magnetism in arc melted Fe-Cu metals with equal atomic ratio of the constituents

NASA Astrophysics Data System (ADS)

Hassnain Jaffari, G.; Aftab, M.; Anjum, D. H.; Cha, Dongkyu; Poirier, Gerald; Ismat Shah, S.

2015-12-01

Composition gradient and phase separation at the nanoscale have been investigated for arc-melted and solidified with equiatomic Fe-Cu. Diffraction studies revealed that Fe and Cu exhibited phase separation with no trace of any mixing. Microscopy studies revealed that immiscible Fe-Cu form dense bulk nanocomposite. The spatial distribution of Fe and Cu showed existence of two distinct regions, i.e., Fe-rich and Cu-rich regions. Fe-rich regions have Cu precipitates of various sizes and different shapes, with Fe forming meshes or channels greater than 100 nm in size. On the other hand, the matrix of Cu-rich regions formed strips with fine strands of nanosized Fe. Macromagnetic response of the system showed ferromagnetic behavior with a magnetic moment being equal to about 2.13 μB/ Fe atom and a bulk like negligible value of coercivity over the temperature range of 5-300 K. Anisotropy constant has been calculated from various laws of approach to saturation, and its value is extracted to be equal to 1350 J/m3. Inhomogeneous strain within the Cu and Fe crystallites has been calculated for the (unannealed) sample solidified after arc-melting. Annealed sample also exhibited local inhomogeneity with removal of inhomogeneous strain and no appreciable change in magnetic character. However, for the annealed sample phase separated Fe exhibited homogenous strain.

Coarsening mechanism of phase separation caused by a double temperature quench in an off-symmetric binary mixture.

PubMed

Sigehuzi, Tomoo; Tanaka, Hajime

2004-11-01

We study phase-separation behavior of an off-symmetric fluid mixture induced by a "double temperature quench." We first quench a system into the unstable region. After a large phase-separated structure is formed, we again quench the system more deeply and follow the pattern-evolution process. The second quench makes the domains formed by the first quench unstable and leads to double phase separation; that is, small droplets are formed inside the large domains created by the first quench. The complex coarsening behavior of this hierarchic structure having two characteristic length scales is studied in detail by using the digital image analysis. We find three distinct time regimes in the time evolution of the structure factor of the system. In the first regime, small droplets coarsen with time inside large domains. There a large domain containing small droplets in it can be regarded as an isolated system. Later, however, the coarsening of small droplets stops when they start to interact via diffusion with the large domain containing them. Finally, small droplets disappear due to the Lifshitz-Slyozov mechanism. Thus the observed behavior can be explained by the crossover of the nature of a large domain from the isolated to the open system; this is a direct consequence of the existence of the two characteristic length scales.

Supercritical fluid chromatographic resolution of water soluble isomeric carboxyl/amine terminated peptides facilitated via mobile phase water and ion pair formation.

PubMed

Patel, M A; Riley, F; Ashraf-Khorassani, M; Taylor, L T

2012-04-13

Both analytical scale and preparative scale packed column supercritical fluid chromatography (SFC) have found widespread applicability for chiral separations of multiple polar pharmaceutical candidates. However, SFC is rapidly becoming an achiral technique. More specifically, ion pair SFC is finding greater utility for separation of ionic analytes such as amine salts and organic sulfonates. The key to this success is, in part, the incorporation of additives such as trifluoroacetic acid and ammonium acetate into the mobile phase in association with a wide variety of both bonded silica stationary phases and high purity bare silica. Ion pairing SFC coupled with evaporative light scattering detection and mass spectrometric detection is presented here for the separation of water soluble, uncapped, isomeric peptide pairs that differ in amino acid arrangement. The separation is best achieved on either diol-bonded silica or bare silica with 1-5% (w/w) water as a significant ingredient in the mobile phase. Nitrogenous stationary phases such as 2-ethylpyridine, which had been very successful for the separation of capped peptides failed to yield the desired separation regardless of the mobile phase composition. A HILIC type retention mechanism is postulated for the separation of both isomeric uncapped peptide pairs. Copyright © 2012 Elsevier B.V. All rights reserved.

Low density microcellular foams

DOEpatents

Aubert, James H.; Clough, Roger L.; Curro, John G.; Quintana, Carlos A.; Russick, Edward M.; Shaw, Montgomery T.

1987-01-01

Low density, microporous polymer foams are provided by a process which comprises forming a solution of polymer and a suitable solvent followed by rapid cooling of the solution to form a phase-separated system and freeze the phase-separated system. The phase-separated system comprises a polymer phase and a solvent phase, each of which is substantially continuous within the other. The morphology of the polymer phase prior to and subsequent to freezing determine the morphology of the resultant foam. Both isotropic and anisotropic foams can be produced. If isotropic foams are produced, the polymer and solvent are tailored such that the solution spontaneously phase-separates prior to the point at which any component freezes. The morphology of the resultant polymer phase determines the morphology of the resultant foam and the morphology of the polymer phase is retained by cooling the system at a rate sufficient to freeze one or both components of the system before a change in morphology can occur. Anisotropic foams are produced by forming a solution of polymer and solvent that will not phase separate prior to freezing of one or both components of the solution. In such a process, the solvent typically freezes before phase separation occurs. The morphology of the resultant frozen two-phase system determines the morphology of the resultant foam. The process involves subjecting the solution to essentially one-dimensional cooling. Means for subjecting such a solvent to one-dimensional cooling are also provided. Foams having a density of less than 0.1 g/cc and a uniform cell size of less than 10 .mu.m and a volume such that the foams have a length greater than 1 cm are provided.

Elongated phase separation domains in spin-cast polymer blend thin films characterized using a panoramic image.

PubMed

Zhang, Hong; Okamura, Yosuke

2018-02-14

Polymer thin films with micro/nano-structures can be prepared by a solvent evaporation induced phase separation process via spin-casting a polymer blend, where the elongated phase separation domains are always inevitable. The striation defect, as a thickness nonunifomity in spin-cast films, is generally coexistent with the elongated domains. Herein, the morphologies of polymer blend thin films are recorded from the spin-cast center to the edge in a panoramic view. The elongated domains are inclined to appear at the ridge regions of striations with increasing radial distance and align radially, exhibiting a coupling between the phase separation morphology and the striation defect that may exist. We demonstrate that the formation of elongated domains is not attributed to shape deformation, but is accomplished in situ. A possible model to describe the initiation and evolution of the polymer blend phase separation morphology during spin-casting is proposed.

Cesium vacancy ordering in phase-separated C s x F e 2 - y S e 2

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

Taddei, K. M.; Sturza, M.; Chung, D. Y.

2015-09-01

By simultaneously displaying magnetism and superconductivity in a single phase, the iron based superconductors provide a model system for the study of magnetism’s role in superconductivity. The class of intercalated iron selenide superconductors is unique amongst these in having the additional property of phase separation and coexistence of two distinct phases - one majority phase with iron vacancy ordering and strong antiferromagnetism and the other a poorly understood minority microscopic phase with a contested structure. Adding to the intrigue, the majority phase has never been found to show superconductivity on its own while the minority phase has never been successfullymore » synthesized separate from the majority phase. In order to better understand this minority phase, a series of high quality CsxFe2-ySe2 single crystals with (0.8 ≤ x ≤ 1; 0 ≤ y ≤ 0.3) were grown and studied. Neutron and x-ray powder diffraction performed on ground crystals show the average structure of the minority phase to be I4/mmm, however, the temperature evolution of its lattice parameters shows it to be distinct from the high temperature I4/mmm parent structure. Neutron and x-ray diffraction experiments performed on single crystal samples reveal the presence of previously unobserved discrete superlattice reflections that remove the degeneracy of the Cs sites in both the majority and minority phases and reduce their structural symmetries from body-centered to primitive. Group theoretical analysis in conjunction with structural modeling shows that the observed superlattice reflections originate from a three-dimensional Cs vacancy ordering in the minority phase. This model predicts a 25% vacancy of the Cs site which is consistent with the site’s refined occupancy. Magnetization measurements performed in tandem with neutron single crystal diffraction provide evidence that the minority phase is the host of superconductivity. Our results also reveal a superconducting dome in which the superconducting transition temperature varies as a function of the valence of iron.« less

High-performance liquid chromatographic enantioseparation of unusual isoxazoline-fused 2-aminocyclopentanecarboxylic acids on macrocyclic glycopeptide-based chiral stationary phases.

PubMed

Sipos, László; Ilisz, István; Nonn, Melinda; Fülöp, Ferenc; Pataj, Zoltán; Armstrong, Daniel W; Péter, Antal

2012-04-06

The enantiomers of four unusual isoxazoline-fused 2-aminocyclopentanecarboxylic acids were directly separated on chiral stationary phases containing macrocyclic glycopeptide antibiotics teicoplanin (Astec Chirobiotic T and T2), teicoplanin aglycone (Chirobiotic TAG), vancomycin (Chirobiotic V) and vancomycin aglycone (Chirobiotic VAG) as chiral selectors. The effects of the mobile phase composition, the structure of the analytes and temperature on the separations were investigated. Experiments were performed at constant mobile phase compositions in the temperature range 5-45 °C to study the effects of temperature, and thermodynamic parameters were calculated from plots of lnk or lnα versus 1/T. Some mechanistic aspects of the chiral recognition process are discussed with respect to the structures of the analytes. It was found that the enantiomeric separations were in most cases enthalpy-driven. The sequence of elution of the enantiomers was determined in all cases. Copyright © 2011 Elsevier B.V. All rights reserved.

High-performance liquid chromatographic enantioseparation of monoterpene-based 2-amino carboxylic acids on macrocyclic glycopeptide-based phases.

PubMed

Sipos, László; Ilisz, István; Pataj, Zoltán; Szakonyi, Zsolt; Fülöp, Ferenc; Armstrong, Daniel W; Péter, Antal

2010-10-29

The enantiomers of five monoterpene-based 2-amino carboxylic acids were directly separated on chiral stationary phases containing macrocyclic glycopeptide antibiotics such as teicoplanin (Astec Chirobiotic T and T2) and teicoplanin aglycone (Chirobiotic TAG) as chiral selectors. The effects of pH, the mobile phase composition, the structure of the analyte and temperature on the separations were investigated. Experiments were performed at constant mobile phase compositions in the temperature range 10-40°C to study the effects of temperature and thermodynamic parameters on separations. Apparent thermodynamic parameters and T(iso) values were calculated from plots of ln k or ln α versus 1/T. Some mechanistic aspects of the chiral recognition process are discussed with respect to the structures of the analytes. It was found that the enantioseparations were in most cases enthalpy driven. The sequence of elution of the enantiomers was determined in all cases. Copyright © 2010 Elsevier B.V. All rights reserved.

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

Baldini, Maria; Muramatsu, Takaki; Sherafati, Mohammad

Phase separation is a crucial ingredient of the physics of manganites; however, the role of mixed phases in the development of the colossal magnetoresistance (CMR) phenomenon still needs to be clarified. In this paper, we report the realization of CMR in a single-valent LaMnO 3 manganite. We found that the insulator-to-metal transition at 32 GPa is well described using the percolation theory. Pressure induces phase separation, and the CMR takes place at the percolation threshold. A large memory effect is observed together with the CMR, suggesting the presence of magnetic clusters. The phase separation scenario is well reproduced, solving amore » model Hamiltonian. Finally, our results demonstrate in a clean way that phase separation is at the origin of CMR in LaMnO 3.« less

Solvent annealing induced phase separation and dewetting in PMMA∕SAN blend film: film thickness and solvent dependence.

PubMed

You, Jichun; Zhang, Shuangshuang; Huang, Gang; Shi, Tongfei; Li, Yongjin

2013-06-28

The competition between "dewetting" and "phase separation" behaviors in polymer blend films attracts significant attention in the last decade. The simultaneous phase separation and dewetting in PMMA∕SAN [poly(methyl methacrylate) and poly(styrene-ran-acrylonitrile)] blend ultrathin films upon solvent annealing have been observed for the first time in our previous work. In this work, film thickness and annealing solvent dependence of phase behaviors in this system has been investigated using atomic force microscopy and grazing incidence small-angle X-ray scattering (GISAXS). On one hand, both vertical phase separation and dewetting take place upon selective solvent vapor annealing, leading to the formation of droplet∕mimic-film structures with various sizes (depending on original film thickness). On the other hand, the whole blend film dewets the substrate and produces dispersed droplets on the silicon oxide upon common solvent annealing. GISAXS results demonstrate the phase separation in the big dewetted droplets resulted from the thicker film (39.8 nm). In contrast, no period structure is detected in small droplets from the thinner film (5.1 nm and 9.7 nm). This investigation indicates that dewetting and phase separation in PMMA∕SAN blend film upon solvent annealing depend crucially on the film thickness and the atmosphere during annealing.

Gas-Liquid Processing in Microchannels

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

TeGrotenhuis, Ward E.; Stenkamp, Victoria S.; Twitchell, Alvin

Processing gases and liquids together in microchannels having at least one dimension <1 mm has unique advantages for rapid heat and mass transfer. One approach for managing the two phases is to use porous structures as wicks within microchannels to segregate the liquid phase from the gas phase. Gas-liquid processing is accomplished by providing a gas flow path and inducing flow of the liquid phase through or along the wick under an induced pressure gradient. A variety of unit operations are enabled, including phase separation, partial condensation, absorption, desorption, and distillation. Results are reported of an investigation of microchannel phasemore » separation in a transparent, single-channel device. Next, heat exchange is integrated with the microchannel wick approach to create a partial condenser that also separates the condensate. Finally, the scale-up to a multi-channel phase separator is described.« less

Phase separation in solutions of monoclonal antibodies and the effect of human serum albumin

PubMed Central

Wang, Ying; Lomakin, Aleksey; Latypov, Ramil F.; Benedek, George B.

2011-01-01

We report the observation of liquid-liquid phase separation in a solution of human monoclonal antibody, IgG2, and the effects of human serum albumin, a major blood protein, on this phase separation. We find a significant reduction of phase separation temperature in the presence of albumin, and a preferential partitioning of the albumin into the antibody-rich phase. We provide a general thermodynamic analysis of the antibody-albumin mixture phase diagram and relate its features to the magnitude of the effective interprotein interactions. Our analysis suggests that additives (HSA in this report), which have moderate attraction with antibody molecules, may be used to forestall undesirable proetin condensation in antibody solutions. Our findings are relevant to understanding the stability of pharmaceutical solutions of antibodies and the mechanisms of cryoglobulinemia. PMID:21921237

Critical review: Injectability of calcium phosphate pastes and cements.

PubMed

O'Neill, R; McCarthy, H O; Montufar, E B; Ginebra, M-P; Wilson, D I; Lennon, A; Dunne, N

2017-03-01

Calcium phosphate cements (CPC) have seen clinical success in many dental and orthopaedic applications in recent years. The properties of CPC essential for clinical success are reviewed in this article, which includes properties of the set cement (e.g. bioresorbability, biocompatibility, porosity and mechanical properties) and unset cement (e.g. setting time, cohesion, flow properties and ease of delivery to the surgical site). Emphasis is on the delivery of calcium phosphate (CaP) pastes and CPC, in particular the occurrence of separation of the liquid and solid components of the pastes and cements during injection; and established methods to reduce this phase separation. In addition a review of phase separation mechanisms observed during the extrusion of other biphasic paste systems and the theoretical models used to describe these mechanisms are discussed. Occurrence of phase separation of calcium phosphate pastes and cements during injection limits their full exploitation as a bone substitute in minimally invasive surgical applications. Due to lack of theoretical understanding of the phase separation mechanism(s), optimisation of an injectable CPC that satisfies clinical requirements has proven difficult. However, phase separation of pastes during delivery has been the focus across several research fields. Therefore in addition to a review of methods to reduce phase separation of CPC and the associated constraints, a review of phase separation mechanisms observed during extrusion of other pastes and the theoretical models used to describe these mechanisms is presented. It is anticipated this review will benefit future attempts to develop injectable calcium phosphate based systems. Crown Copyright © 2016. Published by Elsevier Ltd. All rights reserved.

Study of the Application of Separation Control by Unsteady Excitation to Civil Transport Aircraft

NASA Technical Reports Server (NTRS)

McLean, J. D.; Crouch, J. D.; Stoner, R. C.; Sakurai, S.; Seidel, G. E.; Feifel, W. M.; Rush, H. M.

1999-01-01

This study provides a preliminary assessment of the potential benefits of applying unsteady separation control to transport aircraft. Estimates are given for some of the costs associated with a specific application to high-lift systems. High-leverage areas for future research were identified during the course of the study. The study was conducted in three phases. Phase 1 consisted of a coarse screening of potential applications within the aerodynamics discipline. Potential benefits were identified and in some cases quantified in a preliminary way. Phase 2 concentrated on the application to the wing high-lift system, deemed to have the greatest potential benefit for commercial transports. A team of experts, including other disciplines (i.e. hydraulic, mechanical, and electrical systems, structures, configurations, manufacturing, and finance), assessed the feasibility, benefits, and costs to arrive at estimates of net benefits. In both phases of the study, areas of concern and areas for future research were identified. In phase 3 of this study, the high-leverage areas for future research were prioritized as a guide for future efforts aimed at the application of active flow control to commercial transport aircraft.

Coil planet centrifugation as a means for small particle separation

NASA Technical Reports Server (NTRS)

Herrmann, F. T.

1983-01-01

The coil planet centrifuge uses a centrifugal force field to provide separation of particles based on differences in sedimentation rates by flow through a rotating coiled tube. Three main separations are considered: (1) single phase fresh sheep and human erythrocytes, (2) single phase fixed heep and human erythrocytes, and (3) electrophoretically enhanced single phase fresh sheep and human erythrocytes.

Reversed phase liquid chromatography with UV absorbance and flame ionization detection using a water mobile phase and a cyano propyl stationary phase Analysis of alcohols and chlorinated hydrocarbons.

PubMed

Quigley, W W; Ecker, S T; Vahey, P G; Synovec, R E

1999-10-01

The development of liquid chromatography with a commercially available cyano propyl stationary phase and a 100% water mobile phase is reported. Separations were performed at ambient temperature, simplifying instrumental requirements. Excellent separation efficiency using a water mobile phase was achieved, for example N=18 800, or 75 200 m(-1), was obtained for resorcinol, at a retention factor of k'=4.88 (retention time of 9.55 min at 1 ml min(-1) for a 25 cmx4.6 mm i.d. column, packed with 5 mum diameter particles with the cyano propyl stationary phase). A separation via reversed phase liquid chromatography (RP-LC) with a 100% water mobile phase of six phenols and related compounds was compared to a separation of the same compounds by traditional RP-LC, using octadecylsilane (ODS), i.e. C18, bound to silica and an aqueous mobile phase modified with acetonitrile. Nearly identical analysis time was achieved for the separation of six phenols and related compounds using the cyano propyl stationary phase with a 100% water mobile phase, as compared to traditional RP-LC requiring a relatively large fraction of organic solvent modifier in the mobile phase (25% acetonitrile:75% water). Additional understanding of the retention mechanism with the 100% water mobile phase was obtained by relating measured retention factors of aliphatic alcohols, phenols and related compounds, and chlorinated hydrocarbons to their octanol:water partition coefficients. The retention mechanism is found to be consistent with a RP-LC mechanism coupled with an additional retention effect due to residual hydroxyl groups on the cyano propyl stationary phase. Advantages due to a 100% water mobile phase for the chemical analysis of alcohol mixtures and chlorinated hydrocarbons are reported. By placing an absorbance detector in-series and preceding a novel drop interface to a flame ionization detector (FID), selective detection of a separated mixture of phenols and related compounds and aliphatic alcohols is achieved. The compound class of aliphatic alcohols is selectively and sensitively detected by the drop interface/FID, and the phenols and related compounds are selectively and sensitively detected by absorbance detection at 200 nm. The separation and detection of chlorinated hydrocarbons in a water sample matrix further illustrated the advantages of this methodology. The sensitivity and selectivity of the FID signal for the chlorinated hydrocarbons are significantly better than absorbance detection, even at 200 nm. This methodology is well suited to continuous and automated monitoring of water samples. The applicability of samples initially in an organic solvent matrix is explored, since an organic sample matrix may effect retention and efficiency. Separations in acetonitrile and isopropyl alcohol sample matrices compared well to separations with a water sample matrix.

Purification of biomaterials by phase partitioning

NASA Technical Reports Server (NTRS)

Harris, J. M.

1984-01-01

A technique which is particularly suited to microgravity environments and which is potentially more powerful than electrophoresis is phase partitioning. Phase partitioning is purification by partitioning between the two immiscible aqueous layers formed by solution of the polymers poly(ethylene glycol) and dextran in water. This technique proved to be very useful for separations in one-g but is limited for cells because the cells are more dense than the phase solutions thus tend to sediment to the bottom of the container before reaching equilibrium with the preferred phase. There are three phases to work in this area: synthesis of new polymers for affinity phase partitioning; development of automated apparatus for ground-based separations; and design of apparatus for performing simple phase partitioning space experiments, including examination of mechanisms for separating phases in the absence of gravity.

Continuum theory of phase separation kinetics for active Brownian particles.

PubMed

Stenhammar, Joakim; Tiribocchi, Adriano; Allen, Rosalind J; Marenduzzo, Davide; Cates, Michael E

2013-10-04

Active Brownian particles (ABPs), when subject to purely repulsive interactions, are known to undergo activity-induced phase separation broadly resembling an equilibrium (attraction-induced) gas-liquid coexistence. Here we present an accurate continuum theory for the dynamics of phase-separating ABPs, derived by direct coarse graining, capturing leading-order density gradient terms alongside an effective bulk free energy. Such gradient terms do not obey detailed balance; yet we find coarsening dynamics closely resembling that of equilibrium phase separation. Our continuum theory is numerically compared to large-scale direct simulations of ABPs and accurately accounts for domain growth kinetics, domain topologies, and coexistence densities.

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

Tsvelik, A. M.; Yevtushenko, O. M.

We study the low energy physics of a Kondo chain where electrons from a one-dimensional band interact with magnetic moments via an anisotropic exchange interaction. It is demonstrated that the anisotropy gives rise to two different phases which are separated by a quantum phase transition. In the phase with easy plane anisotropy, Z2 symmetry between sectors with different helicity of the electrons is broken. As a result, localization effects are suppressed and the dc transport acquires (partial) symmetry protection. This effect is similar to the protection of the edge transport in time-reversal invariant topological insulators. The phase with easy axismore » anisotropy corresponds to the Tomonaga-Luttinger liquid with a pronounced spin-charge separation. The slow charge density wave modes have no protection against localizatioin.« less

The use of dihexyldithiocarbamate in reverse-phase HPLC of metal chelates

NASA Astrophysics Data System (ADS)

Fatimah, S. S.; Bahti, H. H.; Hastiawan, I.; Permanasari, A.

2018-05-01

Dialkyldithiocarbamates have long been used as chelating agents in reverse-phase HPLC of transition metals. In the previous study, an alkyl homolog of this type of ligand, namely dihexyldithiocarbamate (DHDTC), was synthesized and characterized. The use of this particular ligand in the revese-phase HPLC of some selected transition metal ions is now reported for the first time. The mobile phase comprising of the flow rate and of the detection, in the separation of the metal chelates of Cd (II), Fe (III), Cu (II), and Co (III), were investigated on a C-18 column. The results showed that dihexylditiocarbamate could be used for separating Cd (II), Fe(III), Cu(II), and Co(III). Therefore, it could be used in simultaneous analysis.

Recovery of Ni Metal from Spent Catalyst with Emulsion Liquid Membrane Using Cyanex 272 as Extractant

NASA Astrophysics Data System (ADS)

Yuliusman; Huda, M.; Ramadhan, I. T.; Farry, A. R.; Wulandari, P. T.; Alfia, R.

2018-03-01

In this study was conducted to recover nickel metal from spent nickel catalyst resulting from hydrotreating process in petroleum industry. The nickel extraction study with the emulsion liquid membrane using Cyanex 272 as an extractant to extract and separate nickel from the feed phase solution. Feed phase solution was preapred from spent catalyst using sulphuric acid. Liquid membrane consists of a kerosene as diluent, a Span 80 as surfactant, a Cyanex 272 as carrier and sulphuric acid solutions have been used as the stripping solution. The important parameters governing the permeation of nickel and their effect on the separation process have been studied. These parameters are surfactant concentration, extractant concentration feed phase pH. The optimum conditions of the emulsion membrane making process is using 0.06 M Cyanex 272, 8% w/v SPAN 80, 0.05 M H2SO4, internal phase extractant / phase volume ratio: 1/1, and stirring speed 1150 rpm for 60 Minute that can produce emulsion membrane with stability level above 90% after 4 hours. In the extraction process with optimum condition pH 6 for feed phase, ratio of phase emulsion/phase of feed: 1/2, and stirring speed 175 rpm for 15 minutes with result 81.51% nickel was extracted.

Phase separation in the t-J model. [in theory of high-temperature superconductors

NASA Technical Reports Server (NTRS)

Emery, V. J.; Lin, H. Q.; Kivelson, S. A.

1990-01-01

A detailed understanding of the motion of 'holes' in an antiferromagnet is of fundamental importance for the theory of high-temperature superconductors. It is shown here that, for the t-J model, dilute holes in an antiferromagnet are unstable against phase separation into a hole-rich and a no-hole phase. When the spin-exchange interaction J exceeds a critical value Jc, the hole-rich phase has no electrons. It is proposed that, for J slightly less than Jc, the hole-rich phase is a low-density superfluid of electron pairs. Phase separation in related models is briefly discussed.

Unmanned Aircraft Systems Human-in-the-Loop Controller and Pilot Acceptability Study: Collision Avoidance, Self-Separation, and Alerting Times (CASSAT)

NASA Technical Reports Server (NTRS)

Comstock, James R., Jr.; Ghatas, Rania W.; Vincent, Michael J.; Consiglio, Maria C.; Munoz, Cesar; Chamberlain, James P.; Volk, Paul; Arthur, Keith E.

2016-01-01

The Federal Aviation Administration (FAA) has been mandated by the Congressional funding bill of 2012 to open the National Airspace System (NAS) to Unmanned Aircraft Systems (UAS). With the growing use of unmanned systems, NASA has established a multi-center "UAS Integration in the NAS" Project, in collaboration with the FAA and industry, and is guiding its research efforts to look at and examine crucial safety concerns regarding the integration of UAS into the NAS. Key research efforts are addressing requirements for detect-and-avoid (DAA), self-separation (SS), and collision avoidance (CA) technologies. In one of a series of human-in-the-loop experiments, NASA Langley Research Center set up a study known as Collision Avoidance, Self-Separation, and Alerting Times (CASSAT). The first phase assessed active air traffic controller interactions with DAA systems and the second phase examined reactions to the DAA system and displays by UAS Pilots at a simulated ground control station (GCS). Analyses of the test results from Phase I and Phase II are presented in this paper. Results from the CASSAT study and previous human-in-the-loop experiments will play a crucial role in the FAA's establishment of rules, regulations, and procedures to safely, efficiently, and effectively integrate UAS into the NAS.

Cesium vacancy ordering in phase-separated C s x F e 2 - y S e 2

DOE PAGES

Taddei, Keith M.; Sturza, M.; Chung, Duck -Yung; ...

2015-09-14

By simultaneously displaying magnetism and superconductivity in a single phase, the iron-based superconductors provide a model system for the study of magnetism's role in superconductivity. The class of intercalated iron selenide superconductors is unique among these in having the additional property of phase separation and coexistence of two distinct phases—one majority phase with iron vacancy ordering and strong antiferromagnetism, and the other a poorly understood minority microscopic phase with a contested structure. Adding to the intrigue, the majority phase has never been found to show superconductivity on its own while the minority phase has never been successfully synthesized separate frommore » the majority phase. In order to better understand this minority phase, a series of high-quality Cs xFe 2–ySe 2 single crystals with (0.8 ≤ x ≤ 1;0 ≤ y ≤ 0.3) were grown and studied. Neutron and x-ray powder diffraction performed on ground crystals show that the average I4/mmm structure of the minority phase is distinctly different from the high-temperature I4/mmm parent structure. Moreover, single-crystal diffraction reveals the presence of discrete superlattice reflections that remove the degeneracy of the Cs sites in both the majority and minority phases and reduce their structural symmetries from body centered to primitive. Group theoretical analysis in conjunction with structural modeling shows that the observed superlattice reflections originate from three-dimensional Cs vacancy ordering. This model predicts a 25% vacancy of the Cs site in the minority phase which is consistent with the site's refined occupancy. Magnetization measurements performed in tandem with neutron single-crystal diffraction provide evidence that the minority phase is the host of superconductivity. Lastly, our results also reveal a superconducting dome in which the superconducting transition temperature varies as a function of the nominal valence of iron.« less

Ionic liquid as a mobile phase additive in high-performance liquid chromatography for the simultaneous determination of eleven fluorescent whitening agents in paper materials.

PubMed

Wang, Qing; Chen, Xianbo; Qiu, Bin; Zhou, Liang; Zhang, Hui; Xie, Juan; Luo, Yan; Wang, Bin

2016-04-01

In the present study, 11 4,4'-diaminostilbene-2,2'-disulfonic acid based fluorescent whitening agents with different numbers of sulfonic acid groups were separated by using an ionic liquid as a mobile phase additive in high-performance liquid chromatography with fluorescence detection. The effects of ionic liquid concentration, pH of mobile phase B, and composition of mobile phase A on the separation of fluorescent whitening agents were systematically investigated. The ionic liquid tetrabutylammonium tetrafluoroborate is superior to tetrabutylammomnium bromide for the separation of the fluorescent whitening agents. The optimal separation conditions were an ionic liquid concentration at 8 mM and the pH of mobile phase B at 8.5 with methanol as mobile phase A. The established method exhibited low limits of detection (0.04-0.07 ng/mL) and wide linearity ranges (0.30-20 ng/mL) with high linear correlation coefficients from 0.9994 to 0.9998. The optimized procedure was applied to analyze target analytes in paper samples with satisfactory results. Eleven target analytes were quantified, and the recoveries of spiked paper samples were in the range of 85-105% with the relative standard deviations from 2.1 to 5.1%. The obtained results indicated that the method was efficient for detection of 11 fluorescent whitening agents. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Extraordinary phase separation and segregation in vent fluids from the southern East Pacific Rise

USGS Publications Warehouse

Von Damm, Karen L.; Lilley, M.D.; Shanks, Wayne C.; Brockington, M.; Bray, A.M.; O'Grady, K. M.; Olson, E.; Graham, A.; Proskurowski, G.

2003-01-01

The discovery of Brandon vent on the southern East Pacific Rise is providing new insights into the controls on midocean ridge hydrothermal vent fluid chemistry. The physical conditions at the time ofsampling (287 bar and 405??C) place the Brandon fluids very close to the critical point of seawater (298 bar and 407??C). This permits in situ study of the effects of near criticalphenomena, which are interpreted to be the primary cause of enhanced transition metal transport in these fluids. Of the five orifices on Brandon sampled, three were venting fluids with less than seawater chlorinity, and two were venting fluids with greater than seawater chlorinity. The liquid phase orifices contain 1.6-1.9 times the chloride content of the vapors. Most other elements, excluding the gases, have this same ratio demonstrating the conservative nature of phase separation and the lack of subsequent water-rock interaction. The vapor and liquid phases vent at the same time from orifices within meters of each other on the Brandon structure. Variations in fluid compositions occur on a time scale of minutes. Our interpretation is that phase separation and segregation must be occurring 'real time' within the sulfide structure itself. Fluids from Brandon therefore provide an unique opportunity to understand in situ phase separation without the overprinting of continued water-rock interaction with the oceanic crust, as well as critical phenomena. ?? 2002 Elsevier Science B.V. All rights reserved.

Separation of O/X Polarization Modes on Oblique Ionospheric Soundings

NASA Astrophysics Data System (ADS)

Harris, T. J.; Cervera, M. A.; Pederick, L. H.; Quinn, A. D.

2017-12-01

The oblique-incidence sounder (OIS) is a well-established instrument for determining the state of the ionosphere, with several advantages over vertical-incidence sounders (VIS). However, the processing and interpretation of OIS ionograms is more complicated than that of VIS ionograms. Due to the Earth's magnetic field, the ionosphere is birefringent at radio frequencies and a VIS or OIS will typically see two distinct ionospheric returns, known as the O and X modes. The separation of these two modes on a VIS, using a polarimetric receive antenna, is a well-established technique. However, this process is more complicated on an OIS due to a variable separation in the phase difference between the two modes, as measured between the two arms of a polarimetric antenna. Using a polarimetric antenna that can be rotated and tilted, we show that this variation in phase separation within an ionogram is caused by the variation in incidence angle, with some configurations leading to greater variation in phase separation. We then develop an algorithm for separating O and X modes in oblique ionograms that can account for the variation in phase separation, and we demonstrate successful separation even in relatively difficult cases. The variation in phase separation can also be exploited to estimate the incident elevation, a technique which may be useful for other applications of HF radio.

Centrifugal partition chromatography in a biorefinery context: Separation of monosaccharides from hydrolysed sugar beet pulp.

PubMed

Ward, David P; Cárdenas-Fernández, Max; Hewitson, Peter; Ignatova, Svetlana; Lye, Gary J

2015-09-11

A critical step in the bioprocessing of sustainable biomass feedstocks, such as sugar beet pulp (SBP), is the isolation of the component sugars from the hydrolysed polysaccharides. This facilitates their subsequent conversion into higher value chemicals and pharmaceutical intermediates. Separation methodologies such as centrifugal partition chromatography (CPC) offer an alternative to traditional resin-based chromatographic techniques for multicomponent sugar separations. Highly polar two-phase systems containing ethanol and aqueous ammonium sulphate are examined here for the separation of monosaccharides present in hydrolysed SBP pectin: l-rhamnose, l-arabinose, d-galactose and d-galacturonic acid. Dimethyl sulfoxide (DMSO) was selected as an effective phase system modifier improving monosaccharide separation. The best phase system identified was ethanol:DMSO:aqueous ammonium sulphate (300gL(-1)) (0.8:0.1:1.8, v:v:v) which enabled separation of the SBP monosaccharides by CPC (200mL column) in ascending mode (upper phase as mobile phase) with a mobile phase flow rate of 8mLmin(-1). A mixture containing all four monosaccharides (1.08g total sugars) in the proportions found in hydrolysed SBP was separated into three main fractions; a pure l-rhamnose fraction (>90%), a mixed l-arabinose/d-galactose fraction and a pure d-galacturonic acid fraction (>90%). The separation took less than 2h demonstrating that CPC is a promising technique for the separation of these sugars with potential for application within an integrated, whole crop biorefinery. Copyright © 2015 The Authors. Published by Elsevier B.V. All rights reserved.

Removal of actinide elements from liquid scintillation cocktail wastes using liquid-liquid extraction and demulsification techniques

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

Foltz, K.; Landsberger, S.; Srinivasan, B.

1994-12-31

A method for the separation of radionuclides with Z greater than 88, from lower-level radioactive wastes (liquid scintillation cocktail or LSC wastes), is described. The method is liquid-liquid extraction (LLX) and demulsification. The actinide elements are removed from the LSC wastes by extraction into an aqueous phase after the cocktail has been demulsified. The aqueous and organic phases are separated, then the wastes type remaining may be incinerated. Future experiments will be performed to study the effects of pH and temperature and to extend the study to wastes containing americium.

Phase-field modeling of diffusional phase behaviors of solid surfaces: A case study of phase-separating Li XFePO 4 electrode particles

DOE PAGES

Heo, Tae Wook; Chen, Long-Qing; Wood, Brandon C.

2015-04-08

In this paper, we present a comprehensive phase-field model for simulating diffusion-mediated kinetic phase behaviors near the surface of a solid particle. The model incorporates elastic inhomogeneity and anisotropy, diffusion mobility anisotropy, interfacial energy anisotropy, and Cahn–Hilliard diffusion kinetics. The free energy density function is formulated based on the regular solution model taking into account the possible solute-surface interaction near the surface. The coherency strain energy is computed using the Fourier-spectral iterative-perturbation method due to the strong elastic inhomogeneity with a zero surface traction boundary condition. Employing a phase-separating Li XFePO 4 electrode particle for Li-ion batteries as a modelmore » system, we perform parametric three-dimensional computer simulations. The model permits the observation of surface phase behaviors that are different from the bulk counterpart. For instance, it reproduces the theoretically well-established surface modes of spinodal decomposition of an unstable solid solution: the surface mode of coherent spinodal decomposition and the surface-directed spinodal decomposition mode. We systematically investigate the influences of major factors on the kinetic surface phase behaviors during the diffusional process. Finally, our simulation study provides insights for tailoring the internal phase microstructure of a particle by controlling the surface phase morphology.« less

Comprehensive lipidomic analysis of human plasma using multidimensional liquid- and gas-phase separations: Two-dimensional liquid chromatography-mass spectrometry vs. liquid chromatography-trapped-ion-mobility-mass spectrometry.

PubMed

Baglai, Anna; Gargano, Andrea F G; Jordens, Jan; Mengerink, Ynze; Honing, Maarten; van der Wal, Sjoerd; Schoenmakers, Peter J

2017-12-29

Recent advancements in separation science have resulted in the commercialization of multidimensional separation systems that provide higher peak capacities and, hence, enable a more-detailed characterization of complex mixtures. In particular, two powerful analytical tools are increasingly used by analytical scientists, namely online comprehensive two-dimensional liquid chromatography (LC×LC, having a second-dimension separation in the liquid phase) and liquid chromatography-ion mobility-spectrometry (LC-IMS, second dimension separation in the gas phase). The goal of the current study was a general assessment of the liquid-chromatography-trapped-ion-mobility-mass spectrometry (LC-TIMS-MS) and comprehensive two-dimensional liquid chromatography-mass spectrometry (LC×LC-MS) platforms for untargeted lipid mapping in human plasma. For the first time trapped-ion-mobility spectrometry (TIMS) was employed for the separation of the major lipid classes and ion-mobility-derived collision-cross-section values were determined for a number of lipid standards. The general effects of a number of influencing parameters have been inspected and possible directions for improvements are discussed. We aimed to provide a general indication and practical guidelines for the analyst to choose an efficient multidimensional separation platform according to the particular requirements of the application. Analysis time, orthogonality, peak capacity, and an indicative measure for the resolving power are discussed as main characteristics for multidimensional separation systems. Copyright © 2017 Elsevier B.V. All rights reserved.

Experimental and Model Studies on Continuous Separation of 2-Phenylpropionic Acid Enantiomers by Enantioselective Liquid-Liquid Extraction in Centrifugal Contactor Separators.

PubMed

Feng, Xiaofeng; Tang, Kewen; Zhang, Pangliang; Yin, Shuangfeng

2016-03-01

Multistage enantioselective liquid-liquid extraction (ELLE) of 2-phenylpropionic acid (2-PPA) enantiomers using hydroxypropyl-β-cyclodextrin (HP-β-CD) as extractant was studied experimentally in a counter-current cascade of centrifugal contactor separators (CCSs). Performance of the process was evaluated by purity (enantiomeric excess, ee) and yield (Y). A multistage equilibrium model was established on the basis of single-stage model for chiral extraction of 2-PPA enantiomers and the law of mass conservation. A series of experiments on the extract phase/washing phase ratio (W/O ratio), extractant concentration, the pH value of aqueous phase, and the number of stages was conducted to verify the multistage equilibrium model. It was found that model predictions were in good agreement with the experimental results. The model was applied to predict and optimize the symmetrical separation of 2-PPA enantiomers. The optimal conditions for symmetric separation involves a W/O ratio of 0.6, pH of 2.5, and HP-β-CD concentration of 0.1 mol L(-1) at a temperature of 278 K, where eeeq (equal enantiomeric excess) can reach up to 37% and Yeq (equal yield) to 69%. By simulation and optimization, the minimum number of stages was evaluated at 98 and 106 for eeeq > 95% and eeeq > 97%. © 2016 Wiley Periodicals, Inc.

Ductile Glass of Polyrotaxane Toughened by Stretch-Induced Intramolecular Phase Separation.

PubMed

Kato, Kazuaki; Nemoto, Kaito; Mayumi, Koichi; Yokoyama, Hideaki; Ito, Kohzo

2017-09-27

A new class of ductile glasses is created from a thermoplastic polyrotaxane. The hard glass, which has a Young's modulus of 1 GPa, shows crazing, necking, and strain hardening with a total elongation of 330%. Stress concentration is prevented through a unique stretch-induced intramolecular phase separation of the cyclic components and the exposed backbone. In situ synchrotron X-ray scattering studies indicate that the backbone polymer chains slip through the cyclic components in the regions where the stress is concentrated.

Effects of Co and Mn doping in K0.8Fe2-ySe2 revisited.

PubMed

Zhou, Tingting; Chen, Xiaolong; Guo, Jiangang; Jin, Shifeng; Wang, Gang; Lai, Xiaofang; Ying, Tianping; Zhang, Han; Shen, Shijie; Wang, Shunchong; Zhu, Kaixing

2013-07-10

Accumulated evidence indicates that phase separation occurs in potassium intercalated iron selenides, a superconducting phase coexisting with the antiferromagnetic phase K2Fe4Se5, the so-called '245 phase'. Here, we report a comparative study of substitution effects by Co and Mn for Fe sites in K0.8Fe2-ySe2 within the phase separation scenario. Our results demonstrate that Co and Mn dopants have distinct differences in occupancy and hence in the suppression mechanism of superconductivity upon doping of Fe sites. In K0.8Fe2-xCoxSe2, Co prefers to occupy the lattice of the superconducting phase and suppresses superconductivity very quickly, obeying the magnetic pair-breaking mechanism or the collapse of the Fermi surface nesting mechanism. In contrast, in K0.8Fe1.7-xMnxSe2, Mn shows no preferential occupancy in the superconducting phase or the 245 phase. The suppression of superconductivity can be attributed to restraining of the superconducting phase and meanwhile inducing another non-superconducting phase by Mn doping.

Fabrication of PVDF-based blend membrane with a thin hydrophilic deposition layer and a network structure supporting layer via the thermally induced phase separation followed by non-solvent induced phase separation process

NASA Astrophysics Data System (ADS)

Wu, Zhiguo; Cui, Zhenyu; Li, Tianyu; Qin, Shuhao; He, Benqiao; Han, Na; Li, Jianxin

2017-10-01

A simple strategy of thermally induced phase separation followed by non-solvent induced phase separation (TIPS-NIPS) is reported to fabricate poly (vinylidene fluoride) (PVDF)-based blend membrane. The dissolved poly (styrene-co-maleic anhydride) (SMA) in diluent prevents the crystallization of PVDF during the cooling process and deposites on the established PVDF matrix in the later extraction. Compared with traditional coating technique, this one-step TIPS-NIPS method can not only fabricate a supporting layer with an interconnected network structure even via solid-liquid phase separation of TIPS, but also form a uniform SMA skin layer approximately as thin as 200 nm via surface deposition of NIPS. Besides the better hydrophilicity, what's interesting is that the BSA rejection ratio increases from 48% to 94% with the increase of SMA, which indicates that the separation performance has improved. This strategy can be conveniently extended to the creation of firmly thin layer, surface functionalization and structure controllability of the membrane.

Molar mass fractionation in aqueous two-phase polymer solutions of dextran and poly(ethylene glycol).

PubMed

Zhao, Ziliang; Li, Qi; Ji, Xiangling; Dimova, Rumiana; Lipowsky, Reinhard; Liu, Yonggang

2016-06-24

Dextran and poly(ethylene glycol) (PEG) in phase separated aqueous two-phase systems (ATPSs) of these two polymers, with a broad molar mass distribution for dextran and a narrow molar mass distribution for PEG, were separated and quantified by gel permeation chromatography (GPC). Tie lines constructed by GPC method are in excellent agreement with those established by the previously reported approach based on density measurements of the phases. The fractionation of dextran during phase separation of ATPS leads to the redistribution of dextran of different chain lengths between the two phases. The degree of fractionation for dextran decays exponentially as a function of chain length. The average separation parameters, for both dextran and PEG, show a crossover from mean field behavior to Ising model behavior, as the critical point is approached. Copyright © 2016 Elsevier B.V. All rights reserved.

Liquid-liquid phase separation in aerosol particles: Imaging at the Nanometer Scale

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

O'Brien, Rachel; Wang, Bingbing; Kelly, Stephen T.

2015-04-21

Atmospheric aerosols can undergo phase transitions including liquid-liquid phase separation (LLPS) while responding to changes in the ambient relative humidity (RH). Here, we report results of chemical imaging experiments using environmental scanning electron microscopy (ESEM) and scanning transmission x-ray microscopy (STXM) to investigate the LLPS of micron sized particles undergoing a full hydration-dehydration cycle. Internally mixed particles composed of ammonium sulfate (AS) and either: limonene secondary organic carbon (LSOC), a, 4-dihydroxy-3-methoxybenzeneaceticacid (HMMA), or polyethylene glycol (PEG-400) were studied. Events of LLPS with apparent core-shell particle morphology were observed for all samples with both techniques. Chemical imaging with STXM showed thatmore » both LSOC/AS and HMMA/AS particles were never homogeneously mixed for all measured RH’s above the deliquescence point and that the majority of the organic component was located in the shell. The shell composition was estimated as 65:35 organic: inorganic in LSOC/AS and as 50:50 organic: inorganic for HMMA/AS. PEG-400/AS particles showed fully homogeneous mixtures at high RH and phase separated below 89-92% RH with an estimated 50:50% organic to inorganic mix in the shell. These two chemical imaging techniques are well suited for in-situ analysis of the hygroscopic behavior, phase separation, and surface composition of collected ambient aerosol particles.« less

Polymer depletion-driven cluster aggregation and initial phase separation in charged nanosized colloids

NASA Astrophysics Data System (ADS)

Gögelein, Christoph; Nägele, Gerhard; Buitenhuis, Johan; Tuinier, Remco; Dhont, Jan K. G.

2009-05-01

We study polymer depletion-driven cluster aggregation and initial phase separation in aqueous dispersions of charge-stabilized silica spheres, where the ionic strength and polymer (dextran) concentration are systematically varied, using dynamic light scattering and visual observation. Without polymers and for increasing salt and colloid content, the dispersions become increasingly unstable against irreversible cluster formation. By adding nonadsorbing polymers, a depletion-driven attraction is induced, which lowers the stabilizing Coulomb barrier and enhances the cluster growth rate. The initial growth rate increases with increasing polymer concentration and decreases with increasing polymer molar mass. These observations can be quantitatively understood by an irreversible dimer formation theory based on the classical Derjaguin, Landau, Verwey, and Overbeek pair potential, with the depletion attraction modeled by the Asakura-Oosawa-Vrij potential. At low colloid concentration, we observe an exponential cluster growth rate for all polymer concentrations considered, indicating a reaction-limited aggregation mechanism. At sufficiently high polymer and colloid concentrations, and lower salt content, a gas-liquidlike demixing is observed initially. Later on, the system separates into a gel and fluidlike phase. The experimental time-dependent state diagram is compared to the theoretical equilibrium phase diagram obtained from a generalized free-volume theory and is discussed in terms of an initial reversible phase separation process in combination with irreversible aggregation at later times.

Polymer depletion-driven cluster aggregation and initial phase separation in charged nanosized colloids.

PubMed

Gögelein, Christoph; Nägele, Gerhard; Buitenhuis, Johan; Tuinier, Remco; Dhont, Jan K G

2009-05-28

We study polymer depletion-driven cluster aggregation and initial phase separation in aqueous dispersions of charge-stabilized silica spheres, where the ionic strength and polymer (dextran) concentration are systematically varied, using dynamic light scattering and visual observation. Without polymers and for increasing salt and colloid content, the dispersions become increasingly unstable against irreversible cluster formation. By adding nonadsorbing polymers, a depletion-driven attraction is induced, which lowers the stabilizing Coulomb barrier and enhances the cluster growth rate. The initial growth rate increases with increasing polymer concentration and decreases with increasing polymer molar mass. These observations can be quantitatively understood by an irreversible dimer formation theory based on the classical Derjaguin, Landau, Verwey, and Overbeek pair potential, with the depletion attraction modeled by the Asakura-Oosawa-Vrij potential. At low colloid concentration, we observe an exponential cluster growth rate for all polymer concentrations considered, indicating a reaction-limited aggregation mechanism. At sufficiently high polymer and colloid concentrations, and lower salt content, a gas-liquidlike demixing is observed initially. Later on, the system separates into a gel and fluidlike phase. The experimental time-dependent state diagram is compared to the theoretical equilibrium phase diagram obtained from a generalized free-volume theory and is discussed in terms of an initial reversible phase separation process in combination with irreversible aggregation at later times.

Space cryogenics components based on the thermomechanical effect - Vapor-liquid phase separation

NASA Technical Reports Server (NTRS)

Yuan, S. W. K.; Frederking, T. H. K.

1989-01-01

Applications of the thermomechanical effect has been qualified including incorporation in large-scale space systems in the area of vapor-liquid phase separation (VLPS). The theory of the porous-plug phase separator is developed for the limit of a high thermal impedance of the solid-state grains. Extensions of the theory of nonlinear turbulent flow are presented based on experimental results.

Investigating hygroscopic behavior and phase separation of organic/inorganic mixed phase aerosol particles with FTIR spectroscopy

NASA Astrophysics Data System (ADS)

Zawadowicz, M. A.; Cziczo, D. J.

2013-12-01

Atmospheric aerosol particles can be composed of inorganic salts, such as ammonium sulfate and sodium chloride, and therefore exhibit hygroscopic properties. Many inorganic salts have very well-defined deliquescence and efflorescence points at which they take up and lose water, respectively. For example, the deliquescence relative humidity of pure ammonium sulfate is about 80% and its efflorescence point is about 35%. This behavior of ammonium sulfate is important to atmospheric chemistry because some reactions, such as the hydrolysis of nitrogen pentoxide, occur on aqueous but not crystalline surfaces. Deliquescence and efflorescence of simple inorganic salt particles have been investigated by a variety of methods, such as IR spectroscopy, tandem mobility analysis and electrodynamic balance. Field measurements have shown that atmospheric aerosol are not typically a single inorganic salt, instead they often contain organic as well as inorganic species. Mixed inorganic/organic aerosol particles, while abundant in the atmosphere, have not been studied as extensively. Many recent studies have focused on microscopy techniques that require deposition of the aerosol on a glass slide, possibly changing its surface properties. This project investigates the deliquescence and efflorescence points, phase separation and ability to exchange gas-phase components of mixed organic and inorganic aerosol using a flow tube coupled with FTIR spectroscopy. Ammonium sulfate aerosol mixed with organic polyols with different O:C ratios, including glycerol, 1,2,6-hexanetriol, 1,4-butanediol and 1,5-pentanediol have been investigated. This project aims to study gas-phase exchange in these aerosol systems to determine if exchange is impacted when phase separation occurs.

Temperature-responsive chromatography for the separation of biomolecules.

PubMed

Kanazawa, Hideko; Okano, Teruo

2011-12-09

Temperature-responsive chromatography for the separation of biomolecules utilizing poly(N-isopropylacrylamide) (PNIPAAm) and its copolymer-modified stationary phase is performed with an aqueous mobile phase without using organic solvent. The surface properties and function of the stationary phase are controlled by external temperature changes without changing the mobile-phase composition. This analytical system is based on nonspecific adsorption by the reversible transition of a hydrophilic-hydrophobic PNIPAAm-grafted surface. The driving force for retention is hydrophobic interaction between the solute molecules and the hydrophobized polymer chains on the stationary phase surface. The separation of the biomolecules, such as nucleotides and proteins was achieved by a dual temperature- and pH-responsive chromatography system. The electrostatic and hydrophobic interactions could be modulated simultaneously with the temperature in an aqueous mobile phase, thus the separation system would have potential applications in the separation of biomolecules. Additionally, chromatographic matrices prepared by a surface-initiated atom transfer radical polymerization (ATRP) exhibit a strong interaction with analytes, because the polymerization procedure forms a densely packed polymer, called a polymer brush, on the surfaces. The copolymer brush grafted surfaces prepared by ATRP was an effective tool for separating basic biomolecules by modulating the electrostatic and hydrophobic interactions. Applications of thermally responsive columns for the separations of biomolecules are reviewed here. Copyright © 2011 Elsevier B.V. All rights reserved.

"Phase capture" in amblyopia: the influence function for sampled shape.

PubMed

Levi, Dennis M; Li, Roger W; Klein, Stanley A

2005-06-01

This study was concerned with what stimulus information humans with amblyopia use to judge the shape of simple objects. We used a string of four Gabor patches to define a contour. A fifth, center patch served as the test pattern. The observers' task was to judge the location of the test pattern relative to the contour. The contour was either a straight line, or an arc with positive or negative curvature. We asked whether phase shifts in the inner or outer pairs of patches distributed along the contour influence the perceived shape. That is, we measured the phase shift influence function. Our results, consistent with previous studies, show that amblyopes are imprecise in shape discrimination, showing elevated thresholds for both lines and curves. We found that amblyopes often make much larger perceptual errors (biases) than do normal observers in the absence of phase shifts. These errors tend to be largest for curved shapes and at large separations. In normal observers, shifting the phase of inner patches of the string by 0.25 cycle results in almost complete phase capture (attraction) at the smallest separation (2 lambda), and the capture effect falls off rapidly with separation. A 0.25 cycle shift of the outer pair of patches has a much smaller effect, in the opposite direction (repulsion). While several amblyopic observers showed reduced capture by the phase of the inner patches, to our surprise, several of the amblyopes were sensitive to the phase of the outer patches. We used linear multiple regression to determine the weights of all cues to the task: the carrier phase of the inner patches, carrier phase of the outer patches and the envelope of the outer patches. Compared to normal observers, some amblyopes show a weaker influence of the phase of the inner patches, and a stronger influence of both the phase and envelope of the outer patches. We speculate that this may be a consequence of abnormal "crowding" of the inner patches by the outer ones.

Process boundaries of irreversible scCO2 -assisted phase separation in biphasic whole-cell biocatalysis.

PubMed

Brandenbusch, Christoph; Glonke, Sebastian; Collins, Jonathan; Hoffrogge, Raimund; Grunwald, Klaudia; Bühler, Bruno; Schmid, Andreas; Sadowski, Gabriele

2015-11-01

The formation of stable emulsions in biphasic biotransformations catalyzed by microbial cells turned out to be a major hurdle for industrial implementation. Recently, a cost-effective and efficient downstream processing approach, using supercritical carbon dioxide (scCO2 ) for both irreversible emulsion destabilization (enabling complete phase separation within minutes of emulsion treatment) and product purification via extraction has been proposed by Brandenbusch et al. (2010). One of the key factors for a further development and scale-up of the approach is the understanding of the mechanism underlying scCO2 -assisted phase separation. A systematic approach was applied within this work to investigate the various factors influencing phase separation during scCO2 treatment (that is pressure, exposure of the cells to CO2 , and changes of cell surface properties). It was shown that cell toxification and cell disrupture are not responsible for emulsion destabilization. Proteins from the aqueous phase partially adsorb to cells present at the aqueous-organic interface, causing hydrophobic cell surface characteristics, and thus contribute to emulsion stabilization. By investigating the change in cell-surface hydrophobicity of these cells during CO2 treatment, it was found that a combination of catastrophic phase inversion and desorption of proteins from the cell surface is responsible for irreversible scCO2 mediated phase separation. These findings are essential for the definition of process windows for scCO2 -assisted phase separation in biphasic whole-cell biocatalysis. © 2015 Wiley Periodicals, Inc.

Electronic Phase Separation in the Slightly Underdoped Iron Pnictide Superconductor Ba{sub 1-x}K{sub x}Fe{sub 2}As{sub 2}

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

Park, J. T.; Inosov, D. S.; Sun, G. L.

2009-03-20

Here we present a combined study of the slightly underdoped novel pnictide superconductor Ba{sub 1-x}K{sub x}Fe{sub 2}As{sub 2} by means of x-ray powder diffraction, neutron scattering, muon-spin rotation ({mu}SR), and magnetic force microscopy (MFM). Static antiferromagnetic order sets in below T{sub m}{approx_equal}70 K as inferred from the neutron scattering and zero-field-{mu}SR data. Transverse-field {mu}SR below T{sub c} shows a coexistence of magnetically ordered and nonmagnetic states, which is also confirmed by MFM imaging. We explain such coexistence by electronic phase separation into antiferromagnetic and superconducting- or normal-state regions on a lateral scale of several tens of nanometers. Our findings indicatemore » that such mesoscopic phase separation can be considered an intrinsic property of some iron pnictide superconductors.« less

Dynamic light scattering study on phase separation of a protein-water mixture: Application on cold cataract development in the ocular lens

NASA Astrophysics Data System (ADS)

Petta, V.; Pharmakakis, N.; Papatheodorou, G. N.; Yannopoulos, S. N.

2008-06-01

We present a detailed dynamic light scattering study of the phase separation in the ocular lens emerging during cold cataract development. Cold cataract is a phase separation effect that proceeds via spinodal decomposition of the lens cytoplasm with cooling. The intensity autocorrelation functions of the lens protein content are analyzed with the aid of two methods, providing information on the populations and dynamics of the scattering elements associated with cold cataract. It is found that the temperature dependence of many measurable parameters changes appreciably at the characteristic temperature ˜16±1°C which is associated with the onset of cold cataract. By extending the temperature range of this work to previously inaccessible regimes, i.e., well below the phase separation or coexistence curve at Tcc , we have been able to accurately determine the temperature dependence of the collective and self-diffusion coefficients of proteins near the spinodal. The analysis showed that the dynamics of proteins bears some resemblance to the dynamics of structural glasses, where the apparent activation energy for particle diffusion increases below Tcc , indicating a highly cooperative motion. Application of ideas developed for studying the critical dynamics of binary protein-solvent mixtures, as well as the use of a modified Arrhenius equation, enabled us to estimate the spinodal temperature Tsp of the lens nucleus. The applicability of dynamic light scattering as a noninvasive, early-diagnostic tool for ocular diseases is also demonstrated in light of the findings of the present paper.

Re-entrant phase behavior for systems with competition between phase separation and self-assembly

NASA Astrophysics Data System (ADS)

Reinhardt, Aleks; Williamson, Alexander J.; Doye, Jonathan P. K.; Carrete, Jesús; Varela, Luis M.; Louis, Ard A.

2011-03-01

In patchy particle systems where there is a competition between the self-assembly of finite clusters and liquid-vapor phase separation, re-entrant phase behavior can be observed, with the system passing from a monomeric vapor phase to a region of liquid-vapor phase coexistence and then to a vapor phase of clusters as the temperature is decreased at constant density. Here, we present a classical statistical mechanical approach to the determination of the complete phase diagram of such a system. We model the system as a van der Waals fluid, but one where the monomers can assemble into monodisperse clusters that have no attractive interactions with any of the other species. The resulting phase diagrams show a clear region of re-entrance. However, for the most physically reasonable parameter values of the model, this behavior is restricted to a certain range of density, with phase separation still persisting at high densities.

Colloidally separated samples from Allende residues - Noble gases, carbon and an ESCA-study

NASA Technical Reports Server (NTRS)

Ott, U.; Kronenbitter, J.; Flores, J.; Chang, S.

1984-01-01

Results are presented which strengthen the hypothesis of heterogeneity among the carbon- and nitrogen-bearing phases of the Allende meteorite. These data also highlight the possibility of performing physical separations yielding samples in which some of the noble gas- and carbon-bearing phases are extraordinarily predominant over others. The conclusion, based on mass and isotope balance arguments, that a significant portion of the carbonaceous matter in Allende is likely to be gas-poor or gas-free need not weaken the case for carbonaceous carriers for the major noble gas components. The concept that acid-soluble carbonaceous phases contain a multiplicity of components, each of which may have formed under a multiplicity of different physical-chemical conditions, is reemphasized by the results of the present study.

1st Stage Separation Aerodynamics Of VEGA Launcher

NASA Astrophysics Data System (ADS)

Genito, M.; Paglia, F.; Mogavero, A.; Barbagallo, D.

2011-05-01

VEGA is an European launch vehicle under development by the Prime Contractor ELV S.p.A. in the frame of an ESA contract. It is constituted by four stages, dedicated to the scientific/commercial market of small satellites (300 ÷ 2500 kg) into Low Earth Orbits, with inclinations ranging from 5.2° up to Sun Synchronous Orbits and with altitude ranging from 300 to 1500 km. Aim of this paper is to present a study of flow field due to retro-rockets impingement during the 1st stage VEGA separation phase. In particular the main goal of the present work is to present the aerodynamic activities performed for the justification of the separation phase.

Phase separation of bio-oil produced by co-pyrolysis of corn cobs and polypropylene

NASA Astrophysics Data System (ADS)

Supramono, D.; Julianto; Haqqyana; Setiadi, H.; Nasikin, M.

2017-11-01

In co-pyrolysis of biomass-plastics, bio-oil produced contains both oxygenated and non-oxygenated compounds. High oxygen composition is responsible for instability and low heating value of bio-oil and high acid content for corrosiveness. Aims of the present work are to evaluate possibilities of achieving phase separation between oxygenated and non-oxygenated compounds in bio-oil using a proposed stirred tank reactor and to achieve synergistic effects on bio-oil yield and non-oxygenated compound layer yield. Separation of bio-oil into two layers, i.e. that containing oxygenated compounds (polar phase) and non-oxygenated compounds (non-polar phase) is important to obtain pure non-polar phase ready for the next processing of hydrogenation and used directly as bio-fuel. There has been no research work on co-pyrolysis of biomass-plastic considering possibility of phase separation of bio-oil. The present work is proposing a stirred tank reactor for co-pyrolysis with nitrogen injection, which is capable of tailoring co-pyrolysis conditions leading to low viscosity and viscosity asymmetry, which induce phase separation between polar phase and non-polar phase. The proposed reactor is capable of generating synergistic effect on bio-oil and non-polar yields as the composition of PP in feed is more than 25% weight in which non-polar layers contain only alkanes, alkenes, cycloalkanes and cycloalkenes.

The Development of Novel Nanomaterials for Separation Science

NASA Astrophysics Data System (ADS)

Zewe, Joseph William

Separation efficiency is inversely proportional to the diameter of the particles of the stationary phase. Accordingly, a major aim of current separations research is focused on the reduction of both the diameter and particle-to-particle size variation of sorbent materials utilized as stationary phases. Herein, novel methods for the fabrication and application of various nanoscale stationary phases are described. Electrospinning is a simple and cost-effective method of generating nanofibers; here both polymeric and carbon electrospun nanofibers are applied as sorbent materials. Carbon nanofibers are of particular interest; graphite and glassy carbon are widely utilized in separation science due to their chemical and mechanical stability and unique selectivity. Electrospun carbon nanofibers have proven to be ideal for use as an extractive phase for solid phase microextraction (SPME) and have been successfully coupled to both gas and liquid chromatography. The high surface area nanofibrous mat provides extraction efficiencies for both polar and nonpolar compounds that range from 2-8 times greater than those attainable using currently available commercial SPME fibers. The electrospun nanofibrous SPME phases proved to be very stable when immersed in a range of solvents, demonstrating increased stability relative to conventional liquid SPME coatings. The chemical and mechanical stability of the electrospun carbon nanofiber SPME phases expands the range of compounds that are applicable to SPME while extending the lifetime of the SPME fibers. Molecularly imprinted (MI) electrospun polymeric and carbon nanofibers were also generated using the template molecule dibutyl butyl phosphonate (DBBP), a surrogate for chemical warfare agents. Nicotine was also used as a template molecule. The MI-nanofibers imprinted with DBBP were applied as an adsorbent for SPME. The MI-SPME fibers preferentially adsorbed the DBBP template molecule relative to the non-imprinted SPME fibers, demonstrating that imprinted surfaces containing analyte-specific recognition sites can be produced. MI-nicotine electrospun nanofibers were also studied as a solid phase extraction (SPE) adsorbent for the extraction of nicotine from water. The MI-nanofibers showed a greater extraction efficiency for nicotine relative to their non-imprinted counterparts. Electrospun nanofibers have proven to be effective stationary phases in ultra-thin layer chromatography (UTLC), giving more efficient separations in shorter analysis times than traditional particle-based stationary phases. This technology was further enhanced by aligning the nanofibrous mats in a single direction. Aligned electrospun UTLC (AE-UTLC) devices showed improved performance relative to non-aligned electrospun UTLC phases, demonstrating higher separation efficiency and reduced times of analysis. All currently utilized carbon sorbents, including the carbon nanofibers described in this work, possess at least two different surface sites for interaction with solutes, namely basal-plane and edge-plane sites. It is predicted that a more homogenous carbon surface, consisting entirely of either all-basal or all-edge plane sites, would produce a separation with a significant improvement in chromatographic efficiency. Progress toward homogenous carbon phases and their application and sorption behavior are also discussed.

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.

Formation and Maturation of Phase Separated Liquid Droplets by RNA Binding Proteins

PubMed Central

Lin, Yuan; Protter, David S. W.; Rosen, Michael K.; Parker, Roy

2015-01-01

Eukaryotic cells possess numerous dynamic membrane-less organelles, RNP granules, enriched in RNA and RNA binding proteins containing disordered regions. We demonstrate that the disordered regions of key RNP granule components, and the full-length granule protein hnRNPA1, can phase separate in vitro, producing dynamic liquid droplets. Phase separation is promoted by low salt concentrations or RNA. Over time, the droplets mature to more stable states, as assessed by slowed fluorescence recovery after photobleaching and resistance to salt. Maturation often coincides with formation of fibrous structures. Different disordered domains can co-assemble into phase-separated droplets. These biophysical properties demonstrate a plausible mechanism by which interactions between disordered regions, coupled with RNA binding, could contribute to RNP granule assembly in vivo through promoting phase separation. Progression from dynamic liquids to stable fibers may be regulated to produce cellular structures with diverse physiochemical properties and functions. Misregulation could contribute to diseases involving aberrant RNA granules. PMID:26412307

Direct visualization of phase separation between superconducting and nematic domains in Co-doped CaFe2As2 close to a first-order phase transition

NASA Astrophysics Data System (ADS)

Fente, Antón; Correa-Orellana, Alexandre; Böhmer, Anna E.; Kreyssig, Andreas; Ran, S.; Bud'ko, Sergey L.; Canfield, Paul C.; Mompean, Federico J.; García-Hernández, Mar; Munuera, Carmen; Guillamón, Isabel; Suderow, Hermann

2018-01-01

We show that biaxial strain induces alternating tetragonal superconducting and orthorhombic nematic domains in Co-substituted CaFe2As2 . We use atomic force, magnetic force, and scanning tunneling microscopy to identify the domains and characterize their properties, finding in particular that tetragonal superconducting domains are very elongated, more than several tens of micrometers long and about 30 nm wide; have the same Tc as unstrained samples; and hold vortices in a magnetic field. Thus, biaxial strain produces a phase-separated state, where each phase is equivalent to what is found on either side of the first-order phase transition between antiferromagnetic orthorhombic and superconducting tetragonal phases found in unstrained samples when changing Co concentration. Having such alternating superconducting domains separated by normal conducting domains with sizes of the order of the coherence length opens opportunities to build Josephson junction networks or vortex pinning arrays and suggests that first-order quantum phase transitions lead to nanometric-size phase separation under the influence of strain.

Direct visualization of phase separation between superconducting and nematic domains in Co-doped CaFe 2 As 2 close to a first-order phase transition

DOE PAGES

Fente, Antón; Correa-Orellana, Alexandre; Böhmer, Anna E.; ...

2018-01-09

We show that biaxial strain induces alternating tetragonal superconducting and orthorhombic nematic domains in Co substituted CaFe 2As 2. We use Atomic Force, Magnetic Force and Scanning Tunneling Microscopy (AFM, MFM and STM) to identify the domains and characterize their properties, nding in particular that tetragonal superconducting domains are very elongated, more than several tens of μm long and about 30 nm wide, have the same Tc than unstrained samples and hold vortices in a magnetic eld. Thus, biaxial strain produces a phase separated state, where each phase is equivalent to what is found at either side of the rstmore » order phase transition between antiferromagnetic orthorhombic and superconducting tetragonal phases found in unstrained samples when changing Co concentration. Having such alternating superconducting domains separated by normal conducting domains with sizes of order of the coherence length opens opportunities to build Josephson junction networks or vortex pinning arrays and suggests that first order quantum phase transitions lead to nanometric size phase separation under the influence of strain.« less

Investigation of foam flotation and phase partitioning techniques

NASA Technical Reports Server (NTRS)

Currin, B. L.

1985-01-01

The present status of foam flotation as a separation process is evaluated and limitations for cells and proteins are determined. Possible applications of foam flotation to separations in microgravity are discussed. Application of the fluid mechanical aspects of foam separation techniques is made to phase partitioning in order to investigate the viscous drag forces that may effect the partitioning of cells in a two phase poly(ethylene glycol) and dextran system.

Ternary Phase-Separation Investigation of Sol-Gel Derived Silica from Ethyl Silicate 40

PubMed Central

Wang, Shengnan; Wang, David K.; Smart, Simon; Diniz da Costa, João C.

2015-01-01

A ternary phase-separation investigation of the ethyl silicate 40 (ES40) sol-gel process was conducted using ethanol and water as the solvent and hydrolysing agent, respectively. This oligomeric silica precursor underwent various degrees of phase separation behaviour in solution during the sol-gel reactions as a function of temperature and H2O/Si ratios. The solution composition within the immiscible region of the ES40 phase-separated system shows that the hydrolysis and condensation reactions decreased with decreasing reaction temperature. A mesoporous structure was obtained at low temperature due to weak drying forces from slow solvent evaporation on one hand and formation of unreacted ES40 cages in the other, which reduced network shrinkage and produced larger pores. This was attributed to the concentration of the reactive sites around the phase-separated interface, which enhanced the condensation and crosslinking. Contrary to dense silica structures obtained from sol-gel reactions in the miscible region, higher microporosity was produced via a phase-separated sol-gel system by using high H2O/Si ratios. This tailoring process facilitated further condensation reactions and crosslinking of silica chains, which coupled with stiffening of the network, made it more resistant to compression and densification. PMID:26411484

Spatial patterning of P granules by RNA-induced phase separation of the intrinsically-disordered protein MEG-3

PubMed Central

Smith, Jarrett; Calidas, Deepika; Schmidt, Helen; Lu, Tu; Rasoloson, Dominique; Seydoux, Geraldine

2016-01-01

RNA granules are non-membrane bound cellular compartments that contain RNA and RNA binding proteins. The molecular mechanisms that regulate the spatial distribution of RNA granules in cells are poorly understood. During polarization of the C. elegans zygote, germline RNA granules, called P granules, assemble preferentially in the posterior cytoplasm. We present evidence that P granule asymmetry depends on RNA-induced phase separation of the granule scaffold MEG-3. MEG-3 is an intrinsically disordered protein that binds and phase separates with RNA in vitro. In vivo, MEG-3 forms a posterior-rich concentration gradient that is anti-correlated with a gradient in the RNA-binding protein MEX-5. MEX-5 is necessary and sufficient to suppress MEG-3 granule formation in vivo, and suppresses RNA-induced MEG-3 phase separation in vitro. Our findings suggest that MEX-5 interferes with MEG-3’s access to RNA, thus locally suppressing MEG-3 phase separation to drive P granule asymmetry. Regulated access to RNA, combined with RNA-induced phase separation of key scaffolding proteins, may be a general mechanism for controlling the formation of RNA granules in space and time. DOI: http://dx.doi.org/10.7554/eLife.21337.001 PMID:27914198

Composition and structure of whey protein/gum arabic coacervates.

PubMed

Weinbreck, F; Tromp, R H; de Kruif, C G

2004-01-01

Complex coacervation in whey protein/gum arabic (WP/GA) mixtures was studied as a function of three main key parameters: pH, initial protein to polysaccharide mixing ratio (Pr:Ps)(ini), and ionic strength. Previous studies had already revealed under which conditions a coacervate phase was obtained. This study is aimed at understanding how these parameters influence the phase separation kinetics, the coacervate composition, and the internal coacervate structure. At a defined (Pr:Ps)(ini), an optimum pH of complex coacervation was found (pH(opt)), at which the strength of electrostatic interaction was maximum. For (Pr:Ps)(ini) = 2:1, the phase separation occurred the fastest and the final coacervate volume was the largest at pH(opt) = 4.0. The composition of the coacervate phase was determined after 48 h of phase separation and revealed that, at pH(opt), the coacervate phase was the most concentrated. Varying the (Pr:Ps)(ini) shifted the pH(opt) to higher values when (Pr:Ps)(ini) was increased and to lower values when (Pr:Ps)(ini) was decreased. This phenomenon was due to the level of charge compensation of the WP/GA complexes. Finally, the structure of the coacervate phase was studied with small-angle X-ray scattering (SAXS). SAXS data confirmed that at pH(opt) the coacervate phase was dense and structured. Model calculations revealed that the structure factor of WP induced a peak at Q = 0.7 nm(-1), illustrating that the coacervate phase was more structured, inducing the stronger correlation length of WP molecules. When the pH was changed to more acidic values, the correlation peak faded away, due to a more open structure of the coacervate. A shoulder in the scattering pattern of the coacervates was visible at small Q. This peak was attributed to the presence of residual charges on the GA. The peak intensity was reduced when the strength of interaction was increased, highlighting a greater charge compensation of the polyelectrolyte. Finally, increasing the ionic strength led to a less concentrated, a more heterogeneous, and a less structured coacervate phase, induced by the screening of the electrostatic interactions.

Investigation, comparison and design of chambers used in centrifugal partition chromatography on the basis of flow pattern and separation experiments.

PubMed

Schwienheer, C; Merz, J; Schembecker, G

2015-04-17

In centrifugal partition chromatography (CPC) the separation efficiency is mainly influenced by the hydrodynamic of mobile and stationary phase in the chambers. Thus, the hydrodynamic has to be investigated and understood in order to enhance a CPC separation run. Different chamber geometries have been developed in the past and the influence of several phase systems and CPC operating conditions were investigated for these chambers. However, a direct comparison between the different chamber types has not been performed yet. In order to investigate the direct influence of the chamber design on the hydrodynamic, several chamber designs - partially similar in geometry to commercial available designs - are investigated under standardized conditions in the present study. The results show the influence of geometrical aspects of the chamber design on the hydrodynamic and therewith, on the separation efficiency. As a conclusion of the present study, some ideas for an optimal chamber design for laboratory and industrial purpose are proposed. Copyright © 2015 Elsevier B.V. All rights reserved.

Comprehensive two-dimensional liquid chromatographic analysis of poloxamers.

PubMed

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

2016-04-15

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

Improved Method for the Qualitative Analyses of Palm Oil Carotenes Using UPLC.

PubMed

Ng, Mei Han; Choo, Yuen May

2016-04-01

Palm oil is the richest source of natural carotenes, comprising 500-700 ppm in crude palm oil (CPO). Its concentration is found to be much higher in oil extracted from palm-pressed fiber, a by-product from the milling of oil palm fruits. There are 11 types of carotenes in palm oil, excluding the cis/trans isomers of some of the carotenes. Qualitative separation of these individual carotenes is particularly useful for the identification and confirmation of different types of oil as the carotenes profile is unique to each type of vegetable oil. Previous studies on HPLC separation of the individual palm carotenes reported a total analyses time of up to 100 min using C30 stationary phase. In this study, the separation was completed in <5 min. The qualitative separation was successfully carried out using a commonly used stationary phase, C18. © The Author 2016. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

Combined effects of mobile phase composition and temperature on the retention of phenolic antioxidants on an octylsilica polydentate column.

PubMed

Jandera, Pavel; Vyňuchalová, Kateřina; Nečilová, Kateřina

2013-11-22

Combined effects of temperature and mobile-phase composition on retention and separation selectivity of phenolic acids and flavonoid compounds were studied in liquid chromatography on a polydentate Blaze C8 silica based column. The temperature effects on the retention can be described by van't Hoff equation. Good linearity of lnk versus 1/T graphs indicates that the retention is controlled by a single mechanism in the mobile phase and temperature range studied. Enthalpic and entropic contributions to the retention were calculated from the regression lines. Generally, enthalpic contributions control the retention at lower temperatures and in mobile phases with lower concentrations of methanol in water. Semi-empirical retention models describe the simultaneous effects of temperature and the volume fraction of the organic solvent in the mobile phase. Using the linear free energy-retention model, selective dipolarity/polarizability, hydrogen-bond donor, hydrogen-bond acceptor and molecular size contributions to retention were estimated at various mobile phase compositions and temperatures. In addition to mobile phase gradients, temperature programming can be used to reduce separation times. Copyright © 2013 Elsevier B.V. All rights reserved.

Experimental design for a basic mixture on a fluorinated packing. The effect of composition of the mobile phase.

PubMed

Wang, Y; Harrison, M; Clark, B J

2006-02-10

An optimization methodology is introduced for investigating the separation and the retention behavior of analytes on a new fluorinated reversed-phase packing. Ten basic compounds were selected as test probes to study the predictive models developed by using SPSS and MATLAB software. A two-level orthogonal array design (OAD) was used to extract significant parameters. The significant factors were optimised using a central composite design to obtain the quadratic relationship between the dependent and the independent variables. Using this strategy, response surfaces were derived as the 3D and contour plots, and mathematical models were defined for the separation. The models had a satisfactory coefficient (R(2) > 0.97, n = 16). For the test compounds, the best separation condition was: MeCN/30 mM phosphate buffer pH 7.1(55.5:44.5, v/v) and 10 basic solutes were resolved in 22 min. The significant influence of the concentration of buffer shows that different mechanisms of separation for basic compounds on the fluorinated packing exist compared with a common ODS stationary phase.

Method of separating lignocellulosic material into lignin, cellulose and dissolved sugars

DOEpatents

Black, S.K.; Hames, B.R.; Myers, M.D.

1998-03-24

A method is described for separating lignocellulosic material into (a) lignin, (b) cellulose, and (c) hemicellulose and dissolved sugars. Wood or herbaceous biomass is digested at elevated temperature in a single-phase mixture of alcohol, water and a water-immiscible organic solvent (e.g., a ketone). After digestion, the amount of water or organic solvent is adjusted so that there is phase separation. The lignin is present in the organic solvent, the cellulose is present in a solid pulp phase, and the aqueous phase includes hemicellulose and any dissolved sugars.

Method of separating lignocellulosic material into lignin, cellulose and dissolved sugars

DOEpatents

Black, Stuart K.; Hames, Bonnie R.; Myers, Michele D.

1998-01-01

A method for separating lignocellulosic material into (a) lignin, (b) cellulose, and (c) hemicellulose and dissolved sugars. Wood or herbaceous biomass is digested at elevated temperature in a single-phase mixture of alcohol, water and a water-immiscible organic solvent (e.g., a ketone). After digestion, the amount of water or organic solvent is adjusted so that there is phase separation. The lignin is present in the organic solvent, the cellulose is present in a solid pulp phase, and the aqueous phase includes hemicellulose and any dissolved sugars.

Vacancy-mediated fcc/bcc phase separation in Fe 1-xNi x ultrathin films

DOE PAGES

Mentes, T. O.; Stojic, N.; Vescovo, E.; ...

2016-08-01

The phase separation occurring in Fe-Ni thin lms near the Invar composition is studied by using high resolution spectromicroscopy techniques and density functional theory calculations. Annealed at temperatures around 300 C, Fe 0.70Ni 0.30 lms on W(110) break into micron-sized bcc and fcc domains with compositions in agreement with the bulk Fe-Ni phase diagram. Ni is found to be the di using species in forming the chemical heterogeneity. The experimentally-determined energy barrier of 1.59 0.09 eV is identi ed as the vacancy formation energy via density functional theory calculations. Thus, the principal role of the surface in the phase separationmore » process is attributed to vacancy creation without interstitials.« less

Closed compact Taylor's droplets in a phase-separated lamellar-sponge mixture under shear flow

NASA Astrophysics Data System (ADS)

Courbin, L.; Cristobal, G.; Rouch, J.; Panizza, P.

2001-09-01

We have studied by optical microscopy, small-angle light scattering, and rheology, the behavior under shear flow of a phase-separated lamellar-sponge (Lα - L3) ternary mixture. We observe in the Lα-rich region (ΦLα > 80%) the existence of a Newtonian assembly made of closed compact monodisperse lamellar droplets immersed in the sponge phase. Contrary to the classical onion glassy texture obtained upon shearing Lα phases, the droplet size scales herein as dot gamma-1, the inverse of the shear rate. This result is in good agreement with Taylor's picture. Above a critical shear rate, dot gammac, the droplets organize to form a single colloidal crystal whose lattice size varies as dot gamma-1/3. To the memory of Tess Melissa P.

Magnetic State of Quasiordered Fe-Al Alloys Doped with Ga and B: Magnetic Phase Separation and Spin Order

NASA Astrophysics Data System (ADS)

Voronina, E. V.; Ivanova, A. G.; Arzhnikov, A. K.; Chumakov, A. I.; Chistyakova, N. I.; Pyataev, A. V.; Korolev, A. V.

2018-04-01

Results of structural, magnetic, and Mössbauer studies of quasi ordered alloys Fe65Al35 - x M x ( M x = Ga, B; x = 0, 5 at %) are presented. The magnetic state of examined structurally-single-phase alloys at low temperatures is interpreted from the viewpoint of magnetic phase separation. An explanation is proposed for the observed behavior of magnetic characteristics of Fe65Al35 and Fe65Al30Ga5 in the framework of the model of two magnetic phases, a ferromagnetic-type one and a spin density wave. The boron-doped alloy Fe65Al30B5 is shown to demonstrate behavior that is typical of materials with the ferromagnetic type of ordering.

The effect of hydrostatic pressure on model membrane domain composition and lateral compressibility.

PubMed

Barriga, H M G; Law, R V; Seddon, J M; Ces, O; Brooks, N J

2016-01-07

Phase separation in ternary model membranes is known to occur over a range of temperatures and compositions and can be induced by increasing hydrostatic pressure. We have used small angle X-ray scattering (SAXS) to study phase separation along pre-determined tie lines in dioleoylphosphatidylcholine (DOPC), dipalmitoylphosphatidylcholine (DPPC) and cholesterol (CHOL) mixtures. We can unequivocally distinguish the liquid ordered (Lo) and liquid disordered (Ld) phases in diffraction patterns from biphasic mixtures and compare their lateral compressibility. The variation of tie line endpoints with increasing hydrostatic pressure was determined, at atmospheric pressure and up to 100 MPa. We find an extension and shift of the tie lines towards the DOPC rich region of the phase diagram at increased pressure, this behaviour differs slightly from that reported for decreasing temperature.

[Separation of p-aminobenzenearsonic acid and its oxide by ion-pair reversed-phase high performance liquid chromatography].

PubMed

Kang, J; Ma, X; Meng, L; Ma, D

1999-05-01

To study the separation of p-aminobenzenearsonic acid (PABAA) and its oxide, p-aminophenylarsine oxide (PAPAO), both the absorption spectra were scanned at the wavelengths from 200 nm to 380 nm. PABAA had absorption maximum at 254 nm and PAPAO 258 nm. The effects of salt concentration, column temperature, methanol and ion-pair agent concentrations on the capacity factor were investigated. Compounds of high polarity showed almost no retention on reversed-phase column; as the volume fraction of the methanol decreased from 90% to 10%, the retention time of PABAA gradually increased with broad peak, and partially eluted when methanol volume fraction being below 20%. With temperature rising, the retention time of PABAA was decreased. But PABAA capacity factor can be increased by selecting an appropriate salt concentration for the mobile phase. The cetyltrimethyl and tetrabutyl ammonium ions were separately added as ion-pair agents to the mobile phase containing methanol in phosphate buffer of 10 mmol/L, the changes of retention time were observed. The mechanism of retention based on reversed phase ion-pair model is proposed. Besides, the retention behaviour is also influenced by size exclusion in stationary phase as well as polar interactions with residual silanol group on the silica surface.

Recent development in liquid chromatography stationary phases for separation of Traditional Chinese Medicine components.

PubMed

Jin, Hongli; Liu, Yanfang; Guo, Zhimou; Wang, Jixia; Zhang, Xiuli; Wang, Chaoran; Liang, Xinmiao

2016-10-25

Traditional Chinese Medicine (TCM) is an ancient medical practice which has been used to prevent and cure diseases for thousands of years. TCMs are frequently multi-component systems with mainly unidentified constituents. The study of the chemical compositions of TCMs remains a hotspot of research. Different strategies have been developed to manage the significant complexity of TCMs, in an attempt to determine their constituents. Reversed-phase liquid chromatography (RPLC) is still the method of choice for the separation of TCMs, but has many problems related to limited selectivity. Recently, enormous efforts have been concentrated on the development of efficient liquid chromatography (LC) methods for TCMs, based on selective stationary phases. This can improve the resolution and peak capacity considerably. In addition, high-efficiency stationary phases have been applied in the analysis of TCMs since the invention of ultra high-performance liquid chromatography (UHPLC). This review describes the advances in LC methods in TCM research from 2010 to date, and focuses on novel stationary phases. Their potential in the separation of TCMs using relevant applications is also demonstrated. Copyright © 2016 Elsevier B.V. All rights reserved.

Origin of colossal magnetoresistance in LaMnO 3 manganite

DOE PAGES

Baldini, Maria; Muramatsu, Takaki; Sherafati, Mohammad; ...

2015-08-13

Phase separation is a crucial ingredient of the physics of manganites; however, the role of mixed phases in the development of the colossal magnetoresistance (CMR) phenomenon still needs to be clarified. In this paper, we report the realization of CMR in a single-valent LaMnO 3 manganite. We found that the insulator-to-metal transition at 32 GPa is well described using the percolation theory. Pressure induces phase separation, and the CMR takes place at the percolation threshold. A large memory effect is observed together with the CMR, suggesting the presence of magnetic clusters. The phase separation scenario is well reproduced, solving amore » model Hamiltonian. Finally, our results demonstrate in a clean way that phase separation is at the origin of CMR in LaMnO 3.« less

Cyclohexylamine additives for enhanced peptide separations in reversed phase liquid chromatography.

PubMed

Cole, S R; Dorsey, J G

1997-01-01

While the choice of stationary phase, organic modifier, and gradient strength can have significant effects on biomolecule separations, mobile phase additives can also have a significant effect on the chromatographic selectivity, recovery, efficiency and resolution. Given the importance of stationary phase coverage, the beneficial, silanol-masking properties of amines, and the potential for selectivity modification through ion-pair interactions, cyclohexylamine was examined as a mobile phase additive and compared with triethylamine and trifluoroacetic acid. Greatly improved separation was possible when cyclohexylamine was used as compared with phosphate buffer, and cyclohexylamine did not require purification before use, while triethylamine required distillation before 'clean' chromatograms were obtained.

Phase separation and the formation of cellular bodies

NASA Astrophysics Data System (ADS)

Xu, Bin; Broedersz, Chase P.; Meir, Yigal; Wingreen, Ned S.

Cellular bodies in eukaryotic cells spontaneously assemble to form cellular compartments. Among other functions, these bodies carry out essential biochemical reactions. Cellular bodies form micron-sized structures, which, unlike canonical cell organelles, are not surrounded by membranes. A recent in vitro experiment has shown that phase separation of polymers in solution can explain the formation of cellular bodies. We constructed a lattice-polymer model to capture the essential mechanism leading to this phase separation. We used both analytical and numerical tools to predict the phase diagram of a system of two interacting polymers, including the concentration of each polymer type in the condensed and dilute phase.

Separability studies of construction and demolition waste recycled sand.

PubMed

Ulsen, Carina; Kahn, Henrique; Hawlitschek, Gustav; Masini, Eldon A; Angulo, Sérgio C

2013-03-01

The quality of recycled aggregates from construction and demolition waste (CDW) is strictly related to the content of porous and low strength phases, and specifically to the patches of cement that remain attached to the surface of natural aggregates. This phase increases water absorption and compromises the consistency and strength of concrete made from recycled aggregates. Mineral processing has been applied to CDW recycling to remove the patches of adhered cement paste on coarse recycled aggregates. The recycled fine fraction is usually disregarded due to its high content of porous phases despite representing around 50% of the total waste. This paper focus on laboratory mineral separability studies for removing particles with a high content of cement paste from natural fine aggregate particles (quartz/feldspars). The procedure achieved processing of CDW by tertiary impact crushing to produce sand, followed by sieving and density and magnetic separability studies. The attained results confirmed that both methods were effective in reducing cement paste content and producing significant mass recovery (80% for density concentration and 60% for magnetic separation). The production of recycled sand contributes to the sustainability of the construction environment by reducing both the consumption of raw materials and disposal of CDW, particularly in large Brazilian centers with a low quantity of sand and increasing costs of this material due to long transportation distances. Copyright © 2012 Elsevier Ltd. All rights reserved.

Fast separation of triterpenoid saponins using supercritical fluid chromatography coupled with single quadrupole mass spectrometry.

PubMed

Huang, Yang; Zhang, Tingting; Zhou, Haibo; Feng, Ying; Fan, Chunlin; Chen, Weijia; Crommen, Jacques; Jiang, Zhengjin

2016-03-20

Triterpenoid saponins (TSs) are the most important components of some traditional Chinese medicines (TCMs) and have exhibited valuable pharmacological properties. In this study, a rapid and efficient method was developed for the separation of kudinosides, stauntosides and ginsenosides using supercritical fluid chromatography coupled with single quadrupole mass spectrometry (SFC-MS). The separation conditions for the selected TSs were carefully optimized after the initial screening of eight stationary phases. The best compromise for all compounds in terms of chromatographic performance and MS sensitivity was obtained when water (5-10%) and formic acid (0.05%) were added to the supercritical carbon dioxide/MeOH mobile phase. Beside the composition of the mobile phase, the nature of the make-up solvent for interfacing SFC with MS was also evaluated. Compared to reversed phase liquid chromatography, the SFC approach showed higher resolution and shorter running time. The developed SFC-MS methods were successfully applied to the separation and identification of TSs present in Ilex latifolia Thunb., Panax quinquefolius L. and Panax ginseng C.A. Meyer. These results suggest that this SFC-MS approach could be employed as a useful tool for the quality assessment of natural products containing TSs as active components. Copyright © 2015 Elsevier B.V. All rights reserved.

Densely quaternized poly(arylene ether)s with distinct phase separation for highly anion-conductive membranes

NASA Astrophysics Data System (ADS)

Hu, Yuanfang; Wang, Bingxi; Li, Xiao; Chen, Dongyang; Zhang, Weiying

2018-05-01

To develop high performance anion exchange membranes (AEMs), a novel bisphenol monomer bearing eight benzylmethyl groups at the outer edge of the molecule was synthesized, which after condensation polymerization with various amounts of 4,4‧-dihydroxydiphenylsulfone and 4,4‧-difluorobenzophenone yielded novel poly(arylene ether)s with densely located benzylmethyl groups. These benzylmethyl groups were then converted to quaternary ammonium groups by radical-initiated bromination and quaternization in tandem, leading to the emergence of densely quaternized poly(arylene ether sulfone)s (QA-PAEs) with controlled ion exchange capacities (IECs) ranging from 1.61 to 2.32 mmol g-1. Both small-angle X-ray scattering (SAXS) and transmission electron microscopy (TEM) studies revealed distinct phase separation in the QA-PAEs. The QA-PAE-40 with an IEC of 2.32 mmol g-1 exhibited a Br- conductivity of 9.2 mS cm-1 and a SO42- conductivity of 14.0 mS cm-1 at room temperature, much higher than those of a control membrane with a similar IEC but without obvious phase separation. Therefore, phase separation of AEMs was validated to be advantageous for the efficient conducting of anions. The experimental results also showed that the QA-PAEs were promising AEM materials, especially for non-alkaline applications.

Development of an on-line mixed-mode gel liquid chromatography×reversed phase liquid chromatography method for separation of water extract from Flos Carthami.

PubMed

Wang, Yu-Qing; Tang, Xu; Li, Jia-Fu; Wu, Yun-Long; Sun, Yu-Ying; Fang, Mei-Juan; Wu, Zhen; Wang, Xiu-Min; Qiu, Ying-Kun

2017-10-13

A novel on-line comprehensive two-dimensional liquid chromatography (2D-LC) method by coupling mixed-mode gel liquid chromatography (MMG-LC) with reversed phase liquid chromatography (RPLC) was developed. A mixture of 17 reference compounds was used to study the separation mechanism. A crude water extract of Flos Carthami was applied to evaluate the performance of the novel 2D-LC system. In the first dimension, the extract was eluted with a gradient of water/methanol over a cross-linked dextran gel Sephadex LH-20 column. Meanwhile, the advantages of size exclusion, reversed phase partition and adsorption separation mechanism were exploited before further on-line reversed phase purification on the second dimension. This novel on-line mixed-mode Sephadex LH-20×RPLC method provided higher peak resolution, sample processing ability (2.5mg) and better orthogonality (72.9%) versus RPLC×RPLC and hydrophilic interaction liquid chromatography (HILIC)×RPLC. To the best of our knowledge, this is the first report of a mixed-mode Sephadex LH-20×RPLC separation method with successful applications in on-line mode, which might be beneficial for harvesting targets from complicated medicinal plants. Copyright © 2017 Elsevier B.V. All rights reserved.

Development of Electrospun Nanomaterials and their Applications in Separation Science

NASA Astrophysics Data System (ADS)

Newsome, Toni Elwell

In separations, efficiency is inversely related to the diameter of the sorbent particles of the stationary phase. Thus, materials research in separation science has primarily been directed towards reducing the diameter of the sorbent particle used in the stationary phase. In this dissertation, innovative methods designed for the fabrication and application of electrospun sorbent nanomaterials for separation science are described. Electrospinning is a facile, cost-effective technique that relies on repulsive electrostatic forces to produce nanofibers from a viscoelastic solution. Here, electrospinning is used to generate polymer, carbon, and silica-based nanofibers which are employed as sorbent nanomaterials in extractions and separations. Electrospun carbon nanofibers have proven to be ideal extractive phases for solid-phase microextraction (SPME) when coupled to gas chromatography (GC) for headspace sampling of volatile analytes. Herein, these carbon nanofibers were employed in the direct extraction of nonvolatile analytes and coupled to liquid chromatography (LC) for the first time. The high surface area of the coatings led to enhanced extraction efficiencies; they offered a 3-33 fold increase in efficiency relative to a commercial SPME phase. Carbon nanofibers proved to be stable when immersed in liquids common to LC demonstrating the enhanced stability of these coatings in SPME coupled to LC relative to conventional SPME fibers. The enhanced chemical and mechanical stability of the carbon SPME coatings considerably expanded the range of compounds applicable to SPME and extended the lifetimes of the fibers. Electrospun nanofibers have also proven to be ideal stationary phases in ultra-thin layer chromatography (UTLC). Nanofibers provide faster separations and enhanced separation efficiencies compared to commercial particle-based stationary phases in a relatively short distance. Here, the electrospun-UTLC technology was extended for the first time to nanofibers composed of silica, the most commonly used surface for TLC. An electrospinning method was optimized to produce silica-based nanofibers with the smallest diameter possible (300-380 nm) while maintaining homogenous nanofiber morphology. Highly efficient separations were performed in 15 mm with observed plate heights as low as 8.6 mum. Silica-based nanofibers proved to be chemically stable with a wide variety of TLC reagents demonstrating the enhanced compatibility of these phases with common TLC methods relative to polymer and carbon nanofiber UTLC plates. The extension of electrospun UTLC to silica-based nanofibers vastly expanded the range of analytes and TLC methods which can be used with this technology. The main disadvantage of conventional TLC development methods is that the mobile phase velocity decreases with increasing separation distance. Here, the chromatographic performance of electrospun polymer stationary phases was further improved by using a forced-flow mobile phase in planar electrochromatography (PEC) in which mobile phase velocity does not diminish with increasing distance. Separations were performed on polymer nanofiber UTLC plates in 1-2 min. Compared to UTLC, PEC offered unique selectivity, decreased analysis times (> 4 times faster), and enhanced efficiency (2-3 times lower plate height). In addition, two-dimensional (2D) separations of a complex analyte mixture using UTLC followed by PEC required only 11 min and exhibited a significant increase in separation number (70-77).

Effects of Swirler Shape on Two-Phase Swirling Flow in a Steam Separator

NASA Astrophysics Data System (ADS)

Kataoka, Hironobu; Shinkai, Yusuke; Tomiyama, Akio

Experiments on two-phase swirling flow in a separator are carried out using several swirlers having different vane angles, different hub diameters and different number of vanes to seek a way for improving steam separators of uprated boiling water reactors. Ratios of the separated liquid flow rate to the total liquid flow rate, flow patterns, liquid film thicknesses and pressure drops are measured to examine the effects of swirler shape on air-water two-phase swirling annular flows in a one-fifth scale model of the separator. As a result, the following conclusions are obtained for the tested swirlers: (1) swirler shape scarcely affects the pressure drop in the barrel of the separator, (2) decreasing the vane angle is an effective way for reducing the pressure drop in the diffuser of the separator, and (3) the film thickness at the inlet of the pick-off-ring of the separator is not sensitive to swirler shape, which explains the reason why the separator performance does not depend on swirler shape.

Recovery of cesium

DOEpatents

Izatt, Reed M.; Christensen, James J.; Hawkins, Richard T.

1984-01-01

A process of recovering cesium ions from mixtures of ions containing them and other ions, e.g., a solution of nuclear waste materials, which comprises establishing a separate source phase containing such a mixture of ions, establishing a separate recipient phase, establishing a liquid membrane phase in interfacial contact with said source and recipient phases, said membrane phase containing a ligand, preferably a selected calixarene as depicted in the drawing, maintaining said interfacial contact for a period of time long enough to transport by said ligand a substantial portion of the cesium ion from the source phase to the recipient phase, and recovering the cesium ion from the recipient phase. The separation of the source and recipient phases may be by the membrane phase only, e.g., where these aqueous phases are emulsified as dispersed phases in a continuous membrane phase, or may include a physical barrier as well, e.g., an open-top outer container with an inner open-ended container of smaller cross-section mounted in the outer container with its open bottom end spaced from and above the closed bottom of the outer container so that the membrane phase may fill the outer container to a level above the bottom of the inner container and have floating on its upper surface a source phase and a recipient phase separated by the wall of the inner container as a physical barrier. A preferred solvent for the ligand is a mixture of methylene chloride and carbon tetrachloride.

Phase Separation of Superconducting Phases in the Penson-Kolb-Hubbard Model

NASA Astrophysics Data System (ADS)

Jerzy Kapcia, Konrad; Czart, Wojciech Robert; Ptok, Andrzej

2016-04-01

In this paper, we determine the phase diagrams (for T = 0 as well as T > 0) of the Penson-Kolb-Hubbard model for two dimensional square lattice within Hartree-Fock mean-field theory focusing on an investigation of superconducting phases and on a possibility of the occurrence of the phase separation. We obtain that the phase separation, which is a state of coexistence of two different superconducting phases (with s- and η-wave symmetries), occurs in definite ranges of the electron concentration. In addition, increasing temperature can change the symmetry of the superconducting order parameter (from η-wave into s-wave). The system considered exhibits also an interesting multicritical behaviour including bicritical points. The relevance of the results to experiments for real materials is also discussed.

Growth and Morphology of Phase Separating Supercritical Fluids

NASA Technical Reports Server (NTRS)

Hegseth, John; Beysens, Daniel; Perrot, Francoise; Nikolayev, Vadim; Garrabos, Yves

1996-01-01

The scientific objective is to study the relation between the morphology and the growth kinetics of domains during phase separation. We know from previous experiments performed near the critical point of pure fluids and binary liquids that there are two simple growth laws at late times. The 'fast' growth appears when the volumes of the phases are nearly equal and the droplet pattern is interconnected. In this case the size of the droplets grows linearly in time. The 'slow' growth appears when the pattern of droplets embedded in the majority phase is disconnected. In this case the size of the droplets increases in proportion to time to the power 1/3. The volume fraction of the minority phase is a good candidate to determine this change of behavior. All previous attempts to vary the volume fraction in a single experimental cell have failed because of the extreme experimental difficulties.

Integral Engine Inlet Particle Separator. Volume 2. Design Guide

DTIC Science & Technology

1975-08-01

herein will be used in the design of integral inlet particle separators for future Army aircraft gas turbine engines . Apprupriate technical personnel...OF INTEGRAL GAS TURBINE ENGINE SOLID PARTICLE INLET SEPARATORS, PHASE I, FEASIBILITY STUDY AND DESIGN, Pratt and Whitney Aircraft ; USAAVLABS Technical...USAAVLABS Technical Report 70-36, U.S. Army Aviation Materiel Laboratories, Fort Eustis, Virginia, August 1970 AD 876 584. 13. ENGINES , AIRCRAFT

Hydrogen separation through tailored dual phase membranes with nominal composition BaCe0.8Eu0.2O3-δ:Ce0.8Y0.2O2-δ at intermediate temperatures

NASA Astrophysics Data System (ADS)

Ivanova, Mariya E.; Escolástico, Sonia; Balaguer, Maria; Palisaitis, Justinas; Sohn, Yoo Jung; Meulenberg, Wilhelm A.; Guillon, Olivier; Mayer, Joachim; Serra, Jose M.

2016-11-01

Hydrogen permeation membranes are a key element in improving the energy conversion efficiency and decreasing the greenhouse gas emissions from energy generation. The scientific community faces the challenge of identifying and optimizing stable and effective ceramic materials for H2 separation membranes at elevated temperature (400-800 °C) for industrial separations and intensified catalytic reactors. As such, composite materials with nominal composition BaCe0.8Eu0.2O3-δ:Ce0.8Y0.2O2-δ revealed unprecedented H2 permeation levels of 0.4 to 0.61 mL·min-1·cm-2 at 700 °C measured on 500 μm-thick-specimen. A detailed structural and phase study revealed single phase perovskite and fluorite starting materials synthesized via the conventional ceramic route. Strong tendency of Eu to migrate from the perovskite to the fluorite phase was observed at sintering temperature, leading to significant Eu depletion of the proton conducing BaCe0.8Eu0.2O3-δ phase. Composite microstructure was examined prior and after a variety of functional tests, including electrical conductivity, H2-permeation and stability in CO2 containing atmospheres at elevated temperatures, revealing stable material without morphological and structural changes, with segregation-free interfaces and no further diffusive effects between the constituting phases. In this context, dual phase material based on BaCe0.8Eu0.2O3-δ:Ce0.8Y0.2O2-δ represents a very promising candidate for H2 separating membrane in energy- and environmentally-related applications.

Phase diagram of a symmetric electron–hole bilayer system: a variational Monte Carlo study

NASA Astrophysics Data System (ADS)

Sharma, Rajesh O.; Saini, L. K.; Prasad Bahuguna, Bhagwati

2018-05-01

We study the phase diagram of a symmetric electron–hole bilayer system at absolute zero temperature and in zero magnetic field within the quantum Monte Carlo approach. In particular, we conduct variational Monte Carlo simulations for various phases, i.e. the paramagnetic fluid phase, the ferromagnetic fluid phase, the anti-ferromagnetic Wigner crystal phase, the ferromagnetic Wigner crystal phase and the excitonic phase, to estimate the ground-state energy at different values of in-layer density and inter-layer spacing. Slater–Jastrow style trial wave functions, with single-particle orbitals appropriate for different phases, are used to construct the phase diagram in the (r s , d) plane by finding the relative stability of trial wave functions. At very small layer separations, we find that the fluid phases are stable, with the paramagnetic fluid phase being particularly stable at and the ferromagnetic fluid phase being particularly stable at . As the layer spacing increases, we first find that there is a phase transition from the ferromagnetic fluid phase to the ferromagnetic Wigner crystal phase when d reaches 0.4 a.u. at r s   =  20, and before there is a return to the ferromagnetic fluid phase when d approaches 1 a.u. However, for r s   <  20 and a.u., the excitonic phase is found to be stable. We do not find that the anti-ferromagnetic Wigner crystal is stable over the considered range of r s and d. We also find that as r s increases, the critical layer separations for Wigner crystallization increase.

Concurrence and fidelity of a Bose-Fermi mixture in a one-dimensional optical lattice.

PubMed

Ning, Wen-Qiang; Gu, Shi-Jian; Chen, Yu-Guang; Wu, Chang-Qin; Lin, Hai-Qing

2008-06-11

We study the ground-state fidelity and entanglement of a Bose-Fermi mixture loaded in a one-dimensional optical lattice. It is found that the fidelity is able to signal quantum phase transitions between the Luttinger liquid phase, the density-wave phase, and the phase separation state of the system, and the concurrence, as a measure of the entanglement, can be used to signal the transition between the density-wave phase and the Ising phase.

Chromatographic Separations Using Solid-Phase Extraction Cartridges: Separation of Wine Phenolics

NASA Astrophysics Data System (ADS)

Brenneman, Charles A.; Ebeler, Susan E.

1999-12-01

We describe a simple laboratory experiment that demonstrates the principles of chromatographic separation using solid-phase extraction columns and red wine. By adjusting pH and mobile phase composition, the wine is separated into three fractions of differing polarity. The content of each fraction can be monitored by UV-vis spectroscopy. When the experiment is combined with experiments involving HPLC or GC separations, students gain a greater appreciation for and understanding of the highly automated instrumental systems currently available. In addition, they learn about the chemistry of polyphenolic compounds, which are present in many foods and beverages and which are receiving much attention for their potentially beneficial health effects.

Separation of betacyanins from purple flowers of Gomphrena globosa L. by ion-pair high-speed counter-current chromatography.

PubMed

Spórna-Kucab, Aneta; Jagodzińska, Joanna; Wybraniec, Sławomir

2017-03-17

Betacyanins, known as antioxidants and chemopreventive natural compounds with colourful properties, were extracted from purple flowers of Gomphrena globosa L. belonging to the Amaranthaceae family and separated for the first time by ion-pair high-speed counter-current chromatography (HSCCC). The pigments were detected by LC-DAD-ESI-MS/MS technique. Separation of betacyanins (300mg) by HSCCC was accomplished in four solvent systems: tert-butyl methyl ether - butanol - acetonitrile - water (0.7% and 1.0% HFBA - heptafluorobutyric acid - system I and III) and tert-butyl methyl ether - butanol - methanol - water (0.7% and 1.0% HFBA - system II and IV) (2:2:1:5, v/v/v/v) in the head-to-tail mode. The mobile phase (aqueous phase) was run at 2.0ml/min and the column rotation speed was 860rpm. The applied systems enabled to study the influence of HFBA concentration as well as systems polarity on betacyanins separation. Comparison of the systems containing 0.7% HFBA (systems I-II) demonstrates that the replacement of acetonitrile by methanol increases the resolution (R s ) between all betacyanins and does not influence the retention of the stationary phase (S f =76%). Higher concentration of the acid in systems III-IV slightly decreases S f to 71% in the systems with 1.0% HFBA. Comparison of the resolution values for betacyanins in the systems with 0.7% and 1.0% HFBA demonstrates that higher concentration of the acid improves the separation effectiveness for all betacyanins as a result of increasing of the chemical affinity of the pigments to the organic stationary phase in HSCCC. The systems III-IV with 1% HFBA are the most effective for the separation of all the studied betacyanins. Copyright © 2017 Elsevier B.V. All rights reserved.

Sericin Promotes Fibroin Silk I Stabilization Across a Phase-Separation.

PubMed

Kwak, Hyo Won; Ju, Ji Eun; Shin, Munju; Holland, Chris; Lee, Ki Hoon

2017-08-14

Natural silk spinning offers several advantages over the synthetic fiber spinning, although the underlying mechanisms of this process are yet to be fully elucidated. Silkworm silks, specifically B. mori, comprise two main proteins: fibroin, which forms the fiber, and sericin, a coextruded coating that acts as a matrix in the resulting nonwoven composite cocoon. To date, most studies have focused on fibroin's self-assembly and gelation, with the influence of sericin during spinning receiving little to no attention. This study investigates sericin's effects on the self-assembly of fibroin via their natural phase-separation. Through changes in sample opacity, FTIR, and XRD, we report that increasing sericin concentration retards the time to gelation and β-sheet formation of fibroin, causing it to adopt a Silk I conformation. Such findings have important implications for both the natural silk spinning process and any future industrial applications, suggesting that sericin may be able to induce long-range conformational and stability control in silk fibroin, while being in a separate phase, a factor that would facilitate long-term storage or silk feedstocks.

Curvature-induced microswarming and clustering of self-propelled particles

NASA Astrophysics Data System (ADS)

Bruss, Isaac; Glotzer, Sharon

Non-equilibrium active matter systems exhibit many unique phenomena, such as motility-induced phase separation and swarming. However, little is known about how these behaviors depend on the geometry of the environment. To answer this question, we use Brownian dynamics simulations to study the effects of Gaussian curvature on self-propelled particles by confining them to the surface of a sphere. We find that a modest amount of curvature promotes phase separation by altering the shape of a cluster's boundary. Alternatively, particles on surfaces of high curvature experience reduced phase separation and instead form microswarms, where particles share a common orbit. We show that this novel flocking behavior is distinct from other previously studied examples, in that it is not explicitly incorporated into our model through Vicsek-like alignment rules nor torques. Rather, we find that microswarms emerge solely due to the geometric link between orientation and velocity, a property exclusive to surfaces with non-zero Gaussian curvature. These findings reveal the important role of local environment on the global emergent behavior of non-equilibrium systems. Center for Bio-Inspired Engineering (DOE Award # DE-SC0000989).

Effect of particle size distribution on the separation efficiency in liquid chromatography.

PubMed

Horváth, Krisztián; Lukács, Diána; Sepsey, Annamária; Felinger, Attila

2014-09-26

In this work, the influence of the width of particle size distribution (PSD) on chromatographic efficiency is studied. The PSD is described by lognormal distribution. A theoretical framework is developed in order to calculate heights equivalent to a theoretical plate in case of different PSDs. Our calculations demonstrate and verify that wide particle size distributions have significant effect on the separation efficiency of molecules. The differences of fully porous and core-shell phases regarding the influence of width of PSD are presented and discussed. The efficiencies of bimodal phases were also calculated. The results showed that these packings do not have any advantage over unimodal phases. Copyright © 2014 Elsevier B.V. All rights reserved.

High performance liquid chromatography enantioseparation of the novel designed mexiletine derivatives and its analogs.

PubMed

Zheng, Chengzhen; Zhang, Datong; Wu, Qi; Lin, Xianfu

2011-02-01

A series of novel designed mexiletine derivatives and its analogs were prepared, the structures were confirmed by Nuclear Magnetic Resonance (NMR), Fourier Transform Infrared Spectroscopy (FTIR), and Electrospray Ionization-Mass Spectrometry (ESI-MS), and the enantioseparations were performed on polysaccharide-based chiral stationary phase (CSP), Chiralcel OD-H, and Chiralcel OJ-H, under normal-phase mode. The effects of the concentration of isopropanol in the mobile phase were studied, seven of the eight enantiomers got baseline separation on Chiralcel OD-H, and five of the eight enantiomers got successfully separation on Chiralcel OJ-H. The effects of structural features were also discussed. Copyright © 2010 Wiley-Liss, Inc.

Classification of LC columns based on the QSRR method and selectivity toward moclobemide and its metabolites.

PubMed

Plenis, Alina; Olędzka, Ilona; Bączek, Tomasz

2013-05-05

This paper focuses on a comparative study of the column classification system based on the quantitative structure-retention relationships (QSRR method) and column performance in real biomedical analysis. The assay was carried out for the LC separation of moclobemide and its metabolites in human plasma, using a set of 24 stationary phases. The QSRR models established for the studied stationary phases were compared with the column test performance results under two chemometric techniques - the principal component analysis (PCA) and the hierarchical clustering analysis (HCA). The study confirmed that the stationary phase classes found closely related by the QSRR approach yielded comparable separation for moclobemide and its metabolites. Therefore, the QSRR method could be considered supportive in the selection of a suitable column for the biomedical analysis offering the selection of similar or dissimilar columns with a relatively higher certainty. Copyright © 2013 Elsevier B.V. All rights reserved.

Phase-Separated Polyaniline/Graphene Composite Electrodes for High-Rate Electrochemical Supercapacitors.

PubMed

Wu, Jifeng; Zhang, Qin'e; Zhou, An'an; Huang, Zhifeng; Bai, Hua; Li, Lei

2016-12-01

Polyaniline/graphene hydrogel composites with a macroscopically phase-separated structure are prepared. The composites show high specific capacitance and excellent rate performance. Further investigation demonstrates that polyaniline inside the graphene hydrogel has low rate performance, thus a phase-separated structure, in which polyaniline is mainly outside the graphene hydrogel matrix, can enhance the rate performance of the composites. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Device for two-dimensional gas-phase separation and characterization of ion mixtures

DOEpatents

Tang, Keqi [Richland, WA; Shvartsburg, Alexandre A [Richland, WA; Smith, Richard D [Richland, WA

2006-12-12

The present invention relates to a device for separation and characterization of gas-phase ions. The device incorporates an ion source, a field asymmetric waveform ion mobility spectrometry (FAIMS) analyzer, an ion mobility spectrometry (IMS) drift tube, and an ion detector. In one aspect of the invention, FAIMS operating voltages are electrically floated on top of the IMS drift voltage. In the other aspect, the FAIMS/IMS interface is implemented employing an electrodynamic ion funnel, including in particular an hourglass ion funnel. The present invention improves the efficiency (peak capacity) and sensitivity of gas-phase separations; the online FAIMS/IMS coupling creates a fundamentally novel two-dimensional gas-phase separation technology with high peak capacity, specificity, and exceptional throughput.

Effect of liquid crystal birefringence on the opacity and off-axis haze of PDLC films

NASA Astrophysics Data System (ADS)

Pane, S.; Caporusso, M.

1998-02-01

PDLC systems are thin films consisting of a dispersion of liquid crystal micro-droplets in a continuous solid phase of polymer matrix. Application of an electric field on a thin layer of PDLC sandwiched between two transparent on-state. This effect make them useful for a wide variety of applications. Among them, smart windows for architectural is the most popular subject in literature. For this application, the key parameters of performance are the haze and the opacity. There are essentially two technologies used to prepare PDLC films, namely micro-encapsulation and phase separation.In the present work we will show the correlation between the opacity and the off-axis haze in PDLC films prepared with a phase separation technology. We will give the general rule in order to select the liquid crystal properties that allow the preparation of high opacity ad low haze PDLC films. Further study about the control of the parameters which influence the performances of PDLC films prepared with phase separation technology and the difference with the NCAP approach are in progress at our laboratory.

HOT ELUENT CAPILLARY LIQUID CHROMATOGRAPHY USING ZIRCONIA AND TITANIA BASED STATIONARY PHASES. (R825344)

EPA Science Inventory

Abstract

High speed capillary liquid chromatographic separations using a simple home made system constructed from readily available inexpensive components have been studied. Using thermally stable zirconia and titania based packing, the separation of eight alkylbenzene...

Preparative enantiomer separation of dichlorprop with a cinchona-derived chiral selector employing centrifugal partition chromatography and high-performance liquid chromatography: a comparative study.

PubMed

Gavioli, Elena; Maier, Norbert M; Minguillón, Cristina; Lindner, Wolfgang

2004-10-01

A countercurrent chromatography protocol for support-free preparative enantiomer separation of the herbicidal agent 2-(2,4-dichlorphenoxy)propionic acid (dichlorprop) was developed utilizing a purposefully designed, highly enantioselective chiral stationary-phase additive (CSPA) derived from bis-1,4-(dihydroquinidinyl)phthalazine. Guided by liquid-liquid extraction experiments, a solvent system consisting of 10 mM CSPA in methyl tert-butyl ether and 100 mM sodium phosphate buffer (pH 8.0) was identified as a suitable stationary/mobile-phase combination. This solvent system provided an ideal compromise among stationary-phase retention, enantioselectivity, and well-balanced analyte distribution behavior. Using a commercial centrifugal partition chromatography instrument, complete enantiomer separations of up to 366 mg of racemic dichlorprop could be achieved, corresponding to a sample load being equivalent to the molar amount of CSPA employed. Comparison of the preparative performance characteristics of the CPC protocol with that of a HPLC separation using a silica-supported bis-1,4-(dihydroquinidinyl)phthalazine chiral stationary phase CSP revealed comparable loading capacities for both techniques but a significantly lower solvent consumption for CPC. With respect to productivity, HPLC was found to be superior, mainly due to inherent flow rate restrictions of the CPC instrument. Given that further progress in instrumental design and engineering of dedicated, highly enantioselective CSPAs can be achieved, CPC may offer a viable alternative to CSP-based HPLC for preparative-scale enantiomer separation.

An atom probe perspective on phase separation and precipitation in duplex stainless steels

NASA Astrophysics Data System (ADS)

Guo, Wei; Garfinkel, David A.; Tucker, Julie D.; Haley, Daniel; Young, George A.; Poplawsky, Jonathan D.

2016-06-01

Three-dimensional chemical imaging of Fe-Cr alloys showing Fe-rich (α)/Cr-rich (α‧) phase separation is reported using atom probe tomography techniques. The extent of phase separation, i.e., amplitude and wavelength, has been quantitatively assessed using the Langer-Bar-on-Miller, proximity histogram, and autocorrelation function methods for two separate Fe-Cr alloys, designated 2101 and 2205. Although the 2101 alloy possesses a larger wavelength and amplitude after annealing at 427 °C for 100-10 000 h, it exhibits a lower hardness than the 2205 alloy. In addition to this phase separation, ultra-fine Ni-Mn-Si-Cu-rich G-phase precipitates form at the α/α‧ interfaces in both alloys. For the 2101 alloy, Cu clusters act to form a nucleus, around which a Ni-Mn-Si shell develops during the precipitation process. For the 2205 alloy, the Ni and Cu atoms enrich simultaneously and no core-shell chemical distribution was found. This segregation phenomenon may arise from the exact Ni/Cu ratio inside the ferrite. After annealing for 10 000 h, the number density of the G-phase within the 2205 alloy was found to be roughly one order of magnitude higher than in the 2101 alloy. The G-phase precipitates have an additional deleterious effect on the thermal embrittlement, as evaluated by the Ashby-Orowan equation, which explains the discrepancy between the hardness and the rate of phase separation with respect to annealing time (Gladman T 1999 Mater. Sci. Tech. Ser. 15 30-36). ).

An atom probe perspective on phase separation and precipitation in duplex stainless steels

DOE PAGES

Garfinkel, David A.; Tucker, Julie D.; Haley, Daniel A.; ...

2016-05-16

Here, three-dimensional chemical imaging of Fe–Cr alloys showing Fe-rich (α)/Cr-rich (α') phase separation is reported using atom probe tomography techniques. The extent of phase separation, i.e., amplitude and wavelength, has been quantitatively assessed using the Langer-Bar-on-Miller, proximity histogram, and autocorrelation function methods for two separate Fe–Cr alloys, designated 2101 and 2205. Although the 2101 alloy possesses a larger wavelength and amplitude after annealing at 427 °C for 100–10 000 h, it exhibits a lower hardness than the 2205 alloy. In addition to this phase separation, ultra-fine Ni–Mn–Si–Cu-rich G-phase precipitates form at the α/α' interfaces in both alloys. For the 2101more » alloy, Cu clusters act to form a nucleus, around which a Ni–Mn–Si shell develops during the precipitation process. For the 2205 alloy, the Ni and Cu atoms enrich simultaneously and no core–shell chemical distribution was found. This segregation phenomenon may arise from the exact Ni/Cu ratio inside the ferrite. After annealing for 10 000 h, the number density of the G-phase within the 2205 alloy was found to be roughly one order of magnitude higher than in the 2101 alloy. The G-phase precipitates have an additional deleterious effect on the thermal embrittlement, as evaluated by the Ashby–Orowan equation, which explains the discrepancy between the hardness and the rate of phase separation with respect to annealing time (Gladman T 1999 Mater. Sci. Tech. Ser. 15 30–36).« less

Hierarchical multiscale hyperporous block copolymer membranes via tunable dual-phase separation

PubMed Central

Yoo, Seungmin; Kim, Jung-Hwan; Shin, Myoungsoo; Park, Hyungmin; Kim, Jeong-Hoon; Lee, Sang-Young; Park, Soojin

2015-01-01

The rational design and realization of revolutionary porous structures have been long-standing challenges in membrane science. We demonstrate a new class of amphiphilic polystyrene-block-poly(4-vinylpyridine) block copolymer (BCP)–based porous membranes featuring hierarchical multiscale hyperporous structures. The introduction of surface energy–modifying agents and the control of major phase separation parameters (such as nonsolvent polarity and solvent drying time) enable tunable dual-phase separation of BCPs, eventually leading to macro/nanoscale porous structures and chemical functionalities far beyond those accessible with conventional approaches. Application of this BCP membrane to a lithium-ion battery separator affords exceptional improvement in electrochemical performance. The dual-phase separation–driven macro/nanopore construction strategy, owing to its simplicity and tunability, is expected to be readily applicable to a rich variety of membrane fields including molecular separation, water purification, and energy-related devices. PMID:26601212

Molecular dynamics simulation study of the role of evenly spaced poly(ethylene oxide) tethers on the aggregation of C60 fullerenes in water.

PubMed

Bedrov, Dmitry; Smith, Grant D; Li, Liwei

2005-06-07

The aggregation behavior of C60 fullerenes and C60 fullerenes with six symmetrically tethered poly(ethylene oxide) oligomers [(PEO)-6-C60] in aqueous solutions has been studied using implicit solvent molecular dynamics simulations. Our simulations reveal that while the attraction between two (PEO)-6-C60 fullerenes in aqueous solution is stronger and longer range than that between two bare C60 fullerenes, the (PEO)-6-C60 fullerenes do not phase-separate in water but rather aggregate in chain-like clusters at concentrations where unmodified fullerenes completely phase-separate.

Detailed monitoring of two biogas plants and mechanical solid-liquid separation of fermentation residues.

PubMed

Bauer, Alexander; Mayr, Herwig; Hopfner-Sixt, Katharina; Amon, Thomas

2009-06-01

The Austrian "green electricity act" (Okostromgesetz) has led to an increase in biogas power plant size and consequently to an increased use of biomass. A biogas power plant with a generating capacity of 500 kW(el) consumes up to 38,000 kg of biomass per day. 260 ha of cropland is required to produce this mass. The high water content of biomass necessitates a high transport volume for energy crops and fermentation residues. The transport and application of fermentation residues to farmland is the last step in this logistic chain. The use of fermentation residues as fertilizer closes the nutrient cycle and is a central element in the efficient use of biomass for power production. Treatment of fermentation residues by separation into liquid and solid phases may be a solution to the transport problem. This paper presents detailed results from the monitoring of two biogas plants and from the analysis of the separation of fermentation residues. Furthermore, two different separator technologies for the separation of fermentation residues of biogas plants were analyzed. The examined biogas plants correspond to the current technological state of the art and have designs developed specifically for the utilization of energy crops. The hydraulic retention time ranged between 45.0 and 83.7 days. The specific methane yields were 0.40-0.43 m(3)N CH(4) per kg VS. The volume loads ranged between 3.69 and 4.00 kg VS/m(3). The degree of degradation was between 77.3% and 82.14%. The screw extractor separator was better suited for biogas slurry separation than the rotary screen separator. The screw extractor separator exhibited a high throughput and good separation efficiency. The efficiency of slurry separation depended on the dry matter content of the fermentation residue. The higher the dry matter content, the higher the proportion of solid phase after separation. In this project, we found that the fermentation residues could be divided into 79.2% fluid phase with a dry matter content of 4.5% and 20.8% solid phase with a dry matter content of 19.3%. Dry matter, volatile solids and carbon, raw ash and phosphate--in relation to the mass--accumulated strongly in the solid phase. Nitrogen and ammonia nitrogen were slightly enriched in the solid phase. Only the potassium content decreased slightly in the solid phase.

The use of native cation-exchange chromatography to study aggregation and phase separation of monoclonal antibodies

PubMed Central

Chen, Shuang; Lau, Hollis; Brodsky, Yan; Kleemann, Gerd R; Latypov, Ramil F

2010-01-01

This study introduces a novel analytical approach for studying aggregation and phase separation of monoclonal antibodies (mAbs). The approach is based on using analytical scale cation-exchange chromatography (CEX) for measuring the loss of soluble monomer in the case of individual and mixed protein solutions. Native CEX outperforms traditional size-exclusion chromatography in separating complex protein mixtures, offering an easy way to assess mAb aggregation propensity. Different IgG1 and IgG2 molecules were tested individually and in mixtures consisting of up to four protein molecules. Antibody aggregation was induced by four different stress factors: high temperature, low pH, addition of fatty acids, and rigorous agitation. The extent of aggregation was determined from the amount of monomeric protein remaining in solution after stress. Consequently, it was possible to address the role of specific mAb regions in antibody aggregation by co-incubating Fab and Fc fragments with their respective full-length molecules. Our results revealed that the relative contribution of Fab and Fc regions in mAb aggregation is strongly dependent on pH and the stress factor applied. In addition, the CEX-based approach was used to study reversible protein precipitation due to phase separation, which demonstrated its use for a broader range of protein–protein association phenomena. In all cases, the role of Fab and Fc was clearly dissected, providing important information for engineering more stable mAb-based therapeutics. PMID:20512972

Tubing modifications for countercurrent chromatography (CCC): Stationary phase retention and separation efficiency.

PubMed

Englert, Michael; Vetter, Walter

2015-07-16

Countercurrent chromatography (CCC) is a separation technique in which two immiscible liquid phases are used for the preparative purification of synthetic and natural products. In CCC the number of repetitive mixing and de-mixing processes, the retention of the stationary phase and the mass transfer between the liquid phases are significant parameters that influence the resolution and separation efficiency. Limited mass transfer is the main reason for peak broadening and a low number of theoretical plates along with impaired peak resolution in CCC. Hence, technical improvements with regard to column design and tubing modifications is an important aspect to enhance mixing and mass transfer. In this study we constructed a crimping tool which allowed us to make reproducible, semi-automated modifications of conventional round-shaped tubing. Six crimped tubing modifications were prepared, mounted onto multilayer coils which were subsequently installed in the CCC system. The stationary phase retention of the tubing modifications were compared to the conventional system with unmodified tubing in a hydrophobic, an intermediate and a hydrophilic two-phase solvent system. Generally, the tubing modifications provided higher capabilities to retain the stationary phase depending on the solvent system and flow rates. In the intermediate solvent system the separation efficiency was evaluated with a mixture of six alkyl p-hydroxybenzoates. The peak resolution could be increased up to 50% with one of the tubing modifications compared to the unmodified tubing. Using the most convincing tubing modification at fixed values for the stationary phase retention, a reasonable comparison to the unmodified tubing was achieved. The peak width could be reduced up to 49% and a strong positive impact at increased flow rates regarding peak resolution and theoretical plate number was observed compared to unmodified tubing. It could be concluded that the tubing modification enhanced the interphase mixing and mass transfer of the two phases by additional and more vigorous agitation. Copyright © 2015 Elsevier B.V. All rights reserved.

Linear solvation energy relationships in normal phase chromatography based on gradient separations.

PubMed

Wu, Di; Lucy, Charles A

2017-09-22

Coupling the modified Soczewiñski model and one gradient run, a gradient method was developed to build a linear solvation energy relationship (LSER) for normal phase chromatography. The gradient method was tested on dinitroanilinopropyl (DNAP) and silica columns with hexane/dichloromethane (DCM) mobile phases. LSER models built based on the gradient separation agree with those derived from a series of isocratic separations. Both models have similar LSER coefficients and comparable goodness of fit, but the LSER model based on gradient separation required fewer trial and error experiments. Copyright © 2017 Elsevier B.V. All rights reserved.

Development of a passive phase separator for space and earth applications

PubMed Central

Wu, Xiongjun; Loraine, Greg; Hsiao, Chao-Tsung; Chahine, Georges L.

2018-01-01

The limited amount of liquids and gases that can be carried to space makes it imperative to recycle and reuse these fluids for extended human operations. During recycling processes gas and liquid phases are often intermixed. In the absence of gravity, separating gases from liquids is challenging due to the absence of buoyancy. This paper describes development of a passive phase separator that is capable of efficiently and reliably separating gas–liquid mixtures of both high and low void fractions in a wide range of flow rates that is applicable to for both space and earth applications. PMID:29628785

Effect of pressure on the selectivity of polymeric C18 and C30 stationary phases in reversed-phase liquid chromatography. Increased separation of isomeric fatty acid methyl esters, triacylglycerols, and tocopherols at high pressure.

PubMed

Okusa, Kensuke; Iwasaki, Yuki; Kuroda, Ikuma; Miwa, Shohei; Ohira, Masayoshi; Nagai, Toshiharu; Mizobe, Hoyo; Gotoh, Naohiro; Ikegami, Tohru; McCalley, David V; Tanaka, Nobuo

2014-04-25

A high-density, polymeric C18 stationary phase (Inertsil ODS-P) or a polymeric C30 phase (Inertsil C30) provided improved resolution of the isomeric fatty acids (FAs), FA methyl esters (FAMEs), triacylglycerols (TAGs), and tocopherols with an increase in pressure of 20-70MPa in reversed-phase HPLC. With respect to isomeric C18 FAMEs with one cis-double bond, ODS-P phase was effective for recognizing the position of a double bond among petroselinic (methyl 6Z-octadecenoate), oleic (methyl 9Z-octadecenoate), and cis-vaccenic (methyl 11Z-octadecenoate), especially at high pressure, but the differentiation between oleic and cis-vaccenic was not achieved by C30 phase regardless of the pressure. A monomeric C18 phase (InertSustain C18) was not effective for recognizing the position of the double bond in monounsaturated FAME, while the separation of cis- and trans-isomers was achieved by any of the stationary phases. The ODS-P and C30 phases provided increased separation for TAGs and β- and γ-tocopherols at high pressure. The transfer of FA, FAME, or TAG molecules from the mobile phase to the ODS-P stationary phase was accompanied by large volume reduction (-30∼-90mL/mol) resulting in a large increase in retention (up to 100% for an increase of 50MPa) and improved isomer separation at high pressure. For some isomer pairs, the ODS-P and C30 provided the opposite elution order, and in each case higher pressure improved the separation. The two stationary phases showed selectivity for the isomers having rigid structures, but only the ODS-P was effective for differentiating the position of a double bond in monounsaturated FAMEs. The results indicate that the improved isomer separation was provided by the increased dispersion interactions between the solute and the binding site of the stationary phase at high pressure. Copyright © 2014 Elsevier B.V. All rights reserved.

Cognitive-Behavioral Therapy with a Six-Year-Old Boy with Separation Anxiety Disorder: A Case Study.

ERIC Educational Resources Information Center

Dia, David A.

2001-01-01

This study examines the use of cognitive-behavioral therapy (CBT) for the treatment of separation anxiety disorder (SAD) in a six-year-old boy who was having at least one panic attack a day. It uses a four-phased program that includes a psychoeducational approach. The outcome studies demonstrated how CBT shows promise as a treatment modality with…

Separation of rare earths from transition metals by liquid-liquid extraction from a molten salt hydrate to an ionic liquid phase.

PubMed

Rout, Alok; Binnemans, Koen

2014-02-28

The solvent extraction of trivalent rare-earth ions and their separation from divalent transition metal ions using molten salt hydrates as the feed phase and an undiluted fluorine-free ionic liquid as the extracting phase were investigated in detail. The extractant was tricaprylmethylammonium nitrate, [A336][NO3], and the hydrated melt was calcium nitrate tetrahydrate, Ca(NO3)2·4H2O. The extraction behavior of rare-earth ions was studied for solutions of individual elements, as well as for mixtures of rare earths in the hydrated melt. The influence of different extraction parameters was investigated: the initial metal loading in the feed phase, percentage of water in the feed solution, equilibration time, and the type of hydrated melt. The extraction of rare earths from Ca(NO3)2·4H2O was compared with extraction from CaCl2·4H2O by [A336][Cl] (Aliquat 336). The nitrate system was found to be the better one. The extraction and separation of rare earths from the transition metals nickel, cobalt and zinc were also investigated. Remarkably high separation factors of rare-earth ions over transition metal ions were observed for extraction from Ca(NO3)2·4H2O by the [A336][NO3] extracting phase. Furthermore, rare-earth ions could be separated efficiently from transition metal ions, even in melts with very high concentrations of transition metal ions. Rare-earth oxides could be directly dissolved in the Ca(NO3)2·4H2O phase in the presence of small amounts of Al(NO3)3·9H2O or concentrated nitric acid. The efficiency of extraction after dissolving the rare-earth oxides in the hydrated nitrate melt was identical to extraction from solutions with rare-earth nitrates dissolved in the molten phase. The stripping of the rare-earth ions from the loaded ionic liquid phase and the reuse of the recycled ionic liquid were also investigated in detail.

Combined heat and mass transfer device for improving separation process

DOEpatents

Tran, Thanh Nhon

1999-01-01

A two-phase small channel heat exchange matrix simultaneously provides for heat transfer and mass transfer between the liquid and vapor phases of a multi-component mixture at a single, predetermined location within a separation column, significantly improving the thermodynamic efficiency of the separation process. The small channel heat exchange matrix is composed of a series of channels having a hydraulic diameter no greater than 5.0 millimeters for conducting a two-phase coolant. In operation, the matrix provides the liquid-vapor contacting surfaces within the separation column, such that heat and mass are transferred simultaneously between the liquid and vapor phases. The two-phase coolant allows for a uniform heat transfer coefficient to be maintained along the length of the channels and across the surface of the matrix. Preferably, a perforated, concave sheet connects each channel to an adjacent channel to facilitate the flow of the liquid and vapor phases within the column and to increase the liquid-vapor contacting surface area.

Combined heat and mass transfer device for improving separation process

DOEpatents

Tran, T.N.

1999-08-24

A two-phase small channel heat exchange matrix simultaneously provides for heat transfer and mass transfer between the liquid and vapor phases of a multi-component mixture at a single, predetermined location within a separation column, significantly improving the thermodynamic efficiency of the separation process. The small channel heat exchange matrix is composed of a series of channels having a hydraulic diameter no greater than 5.0 millimeters for conducting a two-phase coolant. In operation, the matrix provides the liquid-vapor contacting surfaces within the separation column, such that heat and mass are transferred simultaneously between the liquid and vapor phases. The two-phase coolant allows for a uniform heat transfer coefficient to be maintained along the length of the channels and across the surface of the matrix. Preferably, a perforated, concave sheet connects each channel to an adjacent channel to facilitate the flow of the liquid and vapor phases within the column and to increase the liquid-vapor contacting surface area. 12 figs.

Molecular beam epitaxy growth and magnetic properties of Cr-Co-Ga Heusler alloy films

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

Feng, Wuwei, E-mail: wfeng@cugb.edu.cn; Wang, Weihua; Zhao, Chenglong

2015-11-15

We have re-investigated growth and magnetic properties of Cr{sub 2}CoGa films using molecular beam epitaxy technique. Phase separation and precipitate formation were observed experimentally again in agreement with observation of multiple phases separation in sputtered Cr{sub 2}CoGa films by M. Meinert et al. However, significant phase separation could be suppressed by proper control of growth conditions. We showed that Cr{sub 2}CoGa Heusler phase, rather than Co{sub 2}CrGa phase, constitutes the majority of the sample grown on GaAs(001) at 450 {sup o}C. The measured small spin moment of Cr{sub 2}CoGa is in agreement with predicted HM-FCF nature; however, its Curie temperaturemore » is not as high as expected from the theoretical prediction probably due to the off-stoichiometry of Cr{sub 2}CoGa and the existence of the disorders and phase separation.« less

The effect of protein on phase separation in giant unilamellar lipid vesicles.

NASA Astrophysics Data System (ADS)

Hutchison, J. B.; Weis, R. M.; Dinsmore, A. D.

2009-03-01

We explore the coarsening and out of plane curvature (budding) of domains in lipid bilayer vesicles composed of DOPC (unsaturated), PSM (saturated), and cholesterol. Green fluorescent protein (GFP) was added to the membrane in controlled amounts by binding to the Ni-chelating lipid, Ni-DOGS. Vesicles with diameters between 10 and 50 microns were prepared via a standard electroformation procedure. As a sample is lowered through temperature Tmix, a previously homogeneous vesicle phase separates into two fluid phases with distinct compositions. Phase-separated domains have a line tension (energy/length) at the boundary with the major phase which competes with bending energy and lateral tension to determine the overall configuration of the vesicle. Domain budding and coarsening were observed and recorded using both bright field and fluorescence microscopy during temperature scans and with varying concentrations of GFP. The addition of a model protein into our system allows for a broader understanding of the effect of protein, which are ubiquitous in cell membranes, on phase separation, budding, and coarsening.

Equilibrium polymerization models of re-entrant self-assembly

NASA Astrophysics Data System (ADS)

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

2009-04-01

As is well known, liquid-liquid phase separation can occur either upon heating or cooling, corresponding to lower and upper critical solution phase boundaries, respectively. Likewise, self-assembly transitions from a monomeric state to an organized polymeric state can proceed either upon increasing or decreasing temperature, and the concentration dependent ordering temperature is correspondingly called the "floor" or "ceiling" temperature. Motivated by the fact that some phase separating systems exhibit closed loop phase boundaries with two critical points, the present paper analyzes self-assembly analogs of re-entrant phase separation, i.e., re-entrant self-assembly. In particular, re-entrant self-assembly transitions are demonstrated to arise in thermally activated equilibrium self-assembling systems, when thermal activation is more favorable than chain propagation, and in equilibrium self-assembly near an adsorbing boundary where strong competition exists between adsorption and self-assembly. Apparently, the competition between interactions or equilibria generally underlies re-entrant behavior in both liquid-liquid phase separation and self-assembly transitions.

Phase separation of electrons strongly coupled with phonons in cuprates and manganites

NASA Astrophysics Data System (ADS)

Alexandrov, Sasha

2009-03-01

Recent advanced Monte Carlo simulations have not found superconductivity and phase separation in the Hubbard model with on-site repulsive electron-electron correlations. I argue that microscopic phase separations in cuprate superconductors and colossal magnetoresistance (CMR) manganites originate from a strong electron-phonon interaction (EPI) combined with unavoidable disorder. Attractive electron correlations, caused by an almost unretarded EPI, are sufficient to overcome the direct inter-site Coulomb repulsion in these charge-transfer Mott-Hubbard insulators, so that low energy physics is that of small polarons and small bipolarons. They form clusters localized by disorder below the mobility edge, but propagate as the Bloch states above the mobility edge. I identify the Froehlich EPI as the most essential for pairing and phase separation in superconducting layered cuprates. The pairing of oxygen holes into heavy bipolarons in the paramagnetic phase (current-carrier density collapse (CCDC)) explains also CMR and high and low-resistance phase coexistence near the ferromagnetic transition of doped manganites.

Phase behavior and kinetics of phase separation of a nonionic microemulsion of C12E5/water/1-chlorotetradecane upon a temperature quench.

PubMed

Roshan Deen, G; Oliveira, Cristiano L P; Pedersen, Jan Skov

2009-05-21

The phase behavior and phase separation kinetics of a model ternary nonionic microemulsion system composed of pentaethylene glycol dodecyl ether (C12E5), water, and 1-chlorotetradecane were studied. With increasing temperature, the microemulsion exhibits the following rich phase behavior: oil-in-water phase (L1+O), droplet microemulsion phase (L1), lamellar liquid crystalline phase (Lproportional), and sponge-like (liquid) phase (L3). The microemulsion with a fixed surfactant-to-oil volume fraction ratio (Phis/Phio) of 0.81 and droplet volume fraction of 0.087 was perturbed from equilibrium by a temperature quench from the L1 region (24 degrees C) to an unstable region L1+O (13 degrees C), where the excess oil phase is in equilibrium with the microemulsion droplets. The process of phase separation in the unstable region was followed by time-resolved small-angle X-ray scattering (TR-SAXS) and time-resolved turbidity methods. Due to the large range of scattering vector (q=0.004-0.22 A(-1)) that is possible to access with the TR-SAXS method, the growth of the oil droplets and shrinking of the microemulsion droplets as a result of phase separation could be studied simultaneously. By using an advanced polydisperse ellipsoidal hard-sphere model, the experimental curves have been quantitatively analyzed. The microemulsion droplets were modeled as polydisperse core-shell ellipsoidal particles, using molecular constraints, and the oil droplets are modeled as polydisperse spheres. The radius of gyration (Rg) of the growing oil droplets, volume fraction of oil in the microemulsion droplets, and polydispersity were obtained from the fit parameters. The volume equivalent radius at the neutral plane between the surfactant head and tail of the microemulsion droplet decreased from 76 to 51 A, while the radius of oil drop increased to 217 A within the 160 min of the experiment. After about 48 min from the temperature quench, the system reaches a steady state and continues to coarsen at a constant fraction of the oil of 0.51 in the oil phase by Ostwald ripening with the power law dependence of Roil proportional, variant t1/3. The size of the oil droplets determined by the time-resolved turbidity method is in good agreement with that of the TR-SAXS, highlighting the usefulness of the method in the size determination of oil-in-water microemulsions on an absolute scale.

Binary Mixtures of Particles with Different Diffusivities Demix.

PubMed

Weber, Simon N; Weber, Christoph A; Frey, Erwin

2016-02-05

The influence of size differences, shape, mass, and persistent motion on phase separation in binary mixtures has been intensively studied. Here we focus on the exclusive role of diffusivity differences in binary mixtures of equal-sized particles. We find an effective attraction between the less diffusive particles, which are essentially caged in the surrounding species with the higher diffusion constant. This effect leads to phase separation for systems above a critical size: A single close-packed cluster made up of the less diffusive species emerges. Experiments for testing our predictions are outlined.

Phase behavior of stratum corneum lipids in mixed Langmuir-Blodgett monolayers.

PubMed Central

ten Grotenhuis, E; Demel, R A; Ponec, M; Boer, D R; van Miltenburg, J C; Bouwstra, J A

1996-01-01

The lipids found in the bilayers of the stratum corneum fulfill the vital barrier role of mammalian bodies. The main classes of lipids found in stratum corneum are ceramides, cholesterol, and free fatty acids. For an investigation of their phase behavior, mixed Langmuir-Blodgett monolayers of these lipids were prepared. Atomic force microscopy was used to investigate the structure of the monolayers as a function of the monolayer composition. Three different types of ceramide were used: ceramide extracted from pigskin, a commercially available ceramide with several fatty acid chain lengths, and two synthetic ceramides that have only one fatty acid chain length. In pigskin ceramide-cholesterol mixed monolayers phase separation was observed. This phase separation was also found for the commercially available type III Sigma ceramide-cholesterol mixed monolayers with molar ratios ranging from 1:0.1 to 1:1. These monolayers separated into two phases, one composed of the long fatty acid chain fraction of Sigma ceramide III and the other of the short fatty acid chain fraction of Sigma ceramide III mixed with cholesterol. Mixtures with a higher cholesterol content consisted of only one phase. These observations were confirmed by the results obtained with synthetic ceramides, which have only one fatty acid chain length. The synthetic ceramide with a palmitic acid (16:0) chain mixed with cholesterol, and the synthetic ceramide with a lignoceric acid (24:0) chain did not. Free fatty acids showed a preference to mix with one of these phases, depending on their fatty acid chain lengths. The results of this investigation suggest that the model system used in this study is in good agreement with those of other studies concerning the phase behavior of the stratum corneum lipids. By varying the composition of the monolayers one can study the role of each lipid class in detail. Images FIGURE 2 FIGURE 3 FIGURE 4 FIGURE 5 FIGURE 6 PMID:8874014

Phase Behavior of Ritonavir Amorphous Solid Dispersions during Hydration and Dissolution.

PubMed

Purohit, Hitesh S; Taylor, Lynne S

2017-12-01

The aim of this research was to study the interplay of solid and solution state phase transformations during the dissolution of ritonavir (RTV) amorphous solid dispersions (ASDs). RTV ASDs with polyvinylpyrrolidone (PVP), polyvinylpyrrolidone vinyl acetate (PVPVA) and hydroxypropyl methylcellulose acetate succinate (HPMCAS) were prepared at 10-50% drug loading by solvent evaporation. The miscibility of RTV ASDs was studied before and after exposure to 97% relative humidity (RH). Non-sink dissolution studies were performed on fresh and moisture-exposed ASDs. RTV and polymer release were monitored using ultraviolet-visible spectroscopy. Techniques including fluorescence spectroscopy, confocal imaging, scanning electron microscopy (SEM), atomic force microscopy (AFM), differential scanning calorimetry (DSC) and nanoparticle tracking analysis (NTA) were utilized to monitor solid and the solution state phase transformations. All RTV-PVP and RTV-PVPVA ASDs underwent moisture-induced amorphous-amorphous phase separation (AAPS) on high RH storage whereas RTV-HPMCAS ASDs remained miscible. Non-sink dissolution of PVP- and PVPVA-based ASDs at low drug loadings led to rapid RTV and polymer release resulting in concentrations in excess of amorphous solubility, liquid-liquid phase separation (LLPS) and amorphous nanodroplet formation. High drug loading PVP- and PVPVA-based ASDs did not exhibit LLPS upon dissolution as a consequence of extensive AAPS in the hydrated ASD matrix. All RTV-HPMCAS ASDs led to LLPS upon dissolution. RTV ASD dissolution is governed by a competition between the dissolution rate and the rate of phase separation in the hydrated ASD matrix. LLPS was observed for ASDs where the drug release was polymer controlled and only ASDs that remained miscible during the initial phase of dissolution led to LLPS. Techniques such as fluorescence spectroscopy, confocal imaging and SEM were useful in understanding the phase behavior of ASDs upon hydration and dissolution and were helpful in elucidating the mechanism of generation of amorphous nanodroplets.

Coupling Front-End Separations, Ion Mobility Spectrometry, and Mass Spectrometry For Enhanced Multidimensional Biological and Environmental Analyses

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

Zheng, Xueyun; Wojcik, Roza; Zhang, Xing

Ion mobility spectrometry (IMS) is a widely used analytical technique for rapid molecular separations in the gas phase. IMS alone is useful, but its coupling with mass spectrometry (MS) and front-end separations has been extremely beneficial for increasing measurement sensitivity, peak capacity of complex mixtures, and the scope of molecular information in biological and environmental sample analyses. Multiple studies in disease screening and environmental evaluations have even shown these IMS-based multidimensional separations extract information not possible with each technique individually. This review highlights 3-dimensional separations using IMS-MS in conjunction with a range of front-end techniques, such as gas chromatography (GC),more » supercritical fluid chromatography (SFC), liquid chromatography (LC), solid phase extractions (SPE), capillary electrophoresis (CE), field asymmetric ion mobility spectrometry (FAIMS), and microfluidic devices. The origination, current state, various applications, and future capabilities for these multidimensional approaches are described to provide insight into the utility and potential of each technique.« less

The metal-insulator transition in a phase-separated manganite studied by in situ STS

NASA Astrophysics Data System (ADS)

Snijders, P. C.; Gao, M.; Guo, H.; Ward, T. Z.; Gao, H.-J.; Shen, J.; Gai, Z.

2012-02-01

Electronic phase separation (EPS) is a key feature at the heart of the wide variety of electronic and magnetic properties in complex oxides. One consequence of EPS is that electronic transport experiments in bulk materials or 2D films mostly probe the low resistivity electronic phases due to the percolative path of the current. We study oxygen deficient La5/8-xPrxCa3/8M nO3 (LPCMO) thin films using both in situ scanning tunneling spectroscopy (STS) and ex situ transport experiments. The oxygen deficiency is known to decrease the metal-insulator transition (MIT) temperature or even completely suppress the MIT in conventional transport experiments. We show that in situ STS is able to detect the MIT even in systems where conventional transport experiments do not show an MIT at zero magnetic field.

Flow separation in a computational oscillating vocal fold model

NASA Astrophysics Data System (ADS)

Alipour, Fariborz; Scherer, Ronald C.

2004-09-01

A finite-volume computational model that solves the time-dependent glottal airflow within a forced-oscillation model of the glottis was employed to study glottal flow separation. Tracheal input velocity was independently controlled with a sinusoidally varying parabolic velocity profile. Control parameters included flow rate (Reynolds number), oscillation frequency and amplitude of the vocal folds, and the phase difference between the superior and inferior glottal margins. Results for static divergent glottal shapes suggest that velocity increase caused glottal separation to move downstream, but reduction in velocity increase and velocity decrease moved the separation upstream. At the fixed frequency, an increase of amplitude of the glottal walls moved the separation further downstream during glottal closing. Increase of Reynolds number caused the flow separation to move upstream in the glottis. The flow separation cross-sectional ratio ranged from approximately 1.1 to 1.9 (average of 1.47) for the divergent shapes. Results suggest that there may be a strong interaction of rate of change of airflow, inertia, and wall movement. Flow separation appeared to be ``delayed'' during the vibratory cycle, leading to movement of the separation point upstream of the glottal end only after a significant divergent angle was reached, and to persist upstream into the convergent phase of the cycle.

Therapeutic Antibody Engineering To Improve Viscosity and Phase Separation Guided by Crystal Structure.

PubMed

Chow, Chi-Kin; Allan, Barrett W; Chai, Qing; Atwell, Shane; Lu, Jirong

2016-03-07

Antibodies at high concentrations often reveal unanticipated biophysical properties suboptimal for therapeutic development. The purpose of this work was to explore the use of point mutations based on crystal structure information to improve antibody physical properties such as viscosity and phase separation (LLPS) at high concentrations. An IgG4 monoclonal antibody (Mab4) that exhibited high viscosity and phase separation at high concentration was used as a model system. Guided by the crystal structure, four CDR point mutants were made to evaluate the role of hydrophobic and charge interactions on solution behavior. Surprisingly and unpredictably, two of the charge mutants, R33G and N35E, showed a reduction in viscosity and a lower propensity to form LLPS at high concentration compared to the wild-type (WT), while a third charge mutant S28K showed an increased propensity to form LLPS compared to the WT. A fourth mutant, F102H, had reduced hydrophobicity, but unchanged viscosity and phase separation behavior. We further evaluated the correlation of various biophysical measurements including second virial coefficient (A2), interaction parameter (kD), weight-average molecular weight (WAMW), and hydrodynamic diameters (DH), at relatively low protein concentration (4 to 15 mg/mL) to physical properties, such as viscosity and liquid-liquid phase separation (LLPS), at high concentration. Surprisingly, kD measured using dynamic light scattering (DLS) at low antibody concentration correlated better with viscosity and phase separation than did A2 for Mab4. Our results suggest that the high viscosity and phase separation observed at high concentration for Mab4 are mainly driven by charge and not hydrophobicity.

A new submarine oil-water separation system

NASA Astrophysics Data System (ADS)

Cai, Wen-Bin; Liu, Bo-Hong

2017-12-01

In order to solve the oil field losses of environmental problems and economic benefit caused by the separation of lifting production liquid to offshore platforms in the current offshore oil production, from the most basic separation principle, a new oil-water separation system has been processed of adsorption and desorption on related materials, achieving high efficiency and separation of oil and water phases. And the submarine oil-water separation device has been designed. The main structure of the device consists of gas-solid phase separation device, period separating device and adsorption device that completed high efficiency separation of oil, gas and water under the adsorption and desorption principle, and the processing capacity of the device is calculated.

Separation of the stereoisomers of the main metabolite of a non-steroidal anti-inflammatory drug, flobufen, by chiral high-performance liquid chromatography.

PubMed

Wsól, V; Fell, A F; Kvasnicková, E; Hais, I M

1997-02-07

The major metabolite of a novel non-steroidal anti-inflammatory drug, DL-4-(2',4'-difluorobiphenyl-4-yl)-2-oxo-2-methylbutanoic acid (flobufen, I), namely 4-(2',4'-difluorobiphenyl-4-yl)-2-methyl-gamma-butyrolactone (4-dihydroflobufen lactone, III), has four stereoisomers consisting of two racemic pairs of enantiomers. Of three chiral stationary phases tested, Cyclobond I beta-RSP (Astec) (beta-cylodextrin derivatized with R,S-hydroxypropyl) was best able to separate the (+2)(--) racemate, with a liquid phase containing acetonitrile as modifier and triethylamine acetate as buffer. Using the Box-Wilson Central Composite Design for three factors, an optimum combination of pH and concentrations of the modifier and buffer was eventually obtained. A chromatographic response function based on a combination of the Kaiser peak separation function, Pi, and retention time of the second eluting enantiomer, tRL, served as a response criterion for the process of optimization. The optimum conditions developed for the (+2)(--) racemate were also found to be suitable for separating the (+-)(-+) racemate, for which earlier studies had shown the separation to be more facile. Separation of the four stereoisomers of III, for which the chiral chromatographic system optimized in this study is proposed as the second stage, is targeted at a biochemical study of the stereoisomeric metabolism of I.

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.

Two-phase turbine engines. [using gas-liquid mixture accelerated in nozzles

NASA Technical Reports Server (NTRS)

Elliott, D. G.; Hays, L. G.

1976-01-01

A description is given of a two-phase turbine which utilizes a uniform mixture of gas and liquid accelerated in nozzles of the types reported by Elliott and Weinberg (1968). The mixture acts directly on an axial flow or tangential impulse turbine or is separated into gas and liquid streams which operate separately on a gas turbine and a hydraulic turbine. The basic two-phase cycles are examined, taking into account working fluids, aspects of nozzle expansion, details of turbine cycle operation, and the effect of mixture ratio variation. Attention is also given to two-phase nozzle efficiency, two-phase turbine operating characteristics and efficiencies, separator turbines, and impulse turbine experiments.

Prediction of Phase Separation of Immiscible Ga-Tl Alloys

NASA Astrophysics Data System (ADS)

Kim, Yunkyum; Kim, Han Gyeol; Kang, Youn-Bae; Kaptay, George; Lee, Joonho

2017-06-01

Phase separation temperature of Ga-Tl liquid alloys was investigated using the constrained drop method. With this method, density and surface tension were investigated together. Despite strong repulsive interactions, molar volume showed ideal mixing behavior, whereas surface tension of the alloy was close to that of pure Tl due to preferential adsorption of Tl. Phase separation temperatures and surface tension values obtained with this method were close to the theoretically calculated values using three different thermodynamic models.

Aggregation in complex triacylglycerol oils: coarse-grained models, nanophase separation, and predicted x-ray intensities.

PubMed

Quinn, Bonnie; Peyronel, Fernanda; Gordon, Tyler; Marangoni, Alejandro; Hanna, Charles B; Pink, David A

2014-11-19

Triacylglycerols (TAGs) are biologically important molecules which form crystalline nanoplatelets (CNPs) and, ultimately, fat crystal networks in edible oils. Characterizing the self-assembled hierarchies of these networks is important to understanding their functionality and oil binding capacity. We have modelled CNPs in multicomponent oils and studied their aggregation. The oil comprises (a) a liquid component, and (b) components which phase separately on a nano-scale (nano-phase separation) to coat the surfaces of the CNPs impenetrably, either isotropically or anisotropically, with either liquid-like coatings or crystallites, forming a coating of thickness ?. We modelled three cases: (i) liquid?liquid nano-phase separation, (ii) solid?liquid nano-phase separation, with CNPs coated isotropically, and (iii) CNPs coated anisotropically. The models were applied to mixes of tristearin and triolein with fully hydrogenated canola oil, shea butter with high oleic sunflower oil, and cotton seed oil. We performed Monte Carlo simulations, computed structure functions and concluded: (1) three regimes arose: (a) thin coating regime, Δ < 0.0701 u (b) transition regime, 0.0701 u ≤ Δ ≤ 0.0916 u and (c) thick coating regime, Δ > 0.0916 u. (arbitrary units, u) (2) The thin coating regime exhibits 1D TAGwoods, which aggregate, via DLCA/RLCA, into fractal structures which are uniformly distributed in space. (3) In the thick coating regime, for an isotropic coating, TAGwoods are not formed and coated CNPs will not aggregate but will be uniformly distributed in space. For anisotropic coating, TAGwoods can be formed and might form 1D strings but will not form DLCA/RLCA clusters. (4) The regimes are, approximately: thin coating, 0 < Δ < 7.0 nm transition regime, 7.0 < Δ < 9.2 nm and thick coating, Δ > 9.2 nm (5) The minimum minority TAG concentration required to undergo nano-phase separation is, approximately, 0.29% (thin coatings) and 0.94% (thick coatings). Minority components can have substantial effects upon aggregation for concentrations less than 1%.

Stability of Ni-bsed bulk metallic glasses

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

Tokarz, Michelle L; Speakman, Scott A; Porter, Wallace D

Several ternary (Ni{sub x}Nb{sub y}Sn{sub z}) refractory alloy glasses (RAGs) were studied at elevated temperatures in order to assess the stability of the amorphous state, i.e. devitrification, and to identify subsequent phase transformations in these materials. differential scanning calorimetry (DSC) experiments indicated a complex phase transformation sequence with several distinct crystallization and melting events being recorded above the glass transition temperature, T{sub g}. Below T{sub g} the RAG samples were studied with an in situ environmental X-ray furnace facility, which allowed step-wise isothermal ramping experiments commencing at a temperature below the reduced temperature of T/T{sub g} {approx} 0.80. Distinct crystallinemore » phases were observed when T/T{sub g} {approx} 0.84 for ternary RAG alloys, while similar experiments on Zr-based Vit 106 glass alloys did not reveal any apparent phase separation until T/T{sub g} {approx} 0.96. The phase separation kinetics followed an Arrhenius type of relationship with Ni{sub 3}Sn, and Nb{sub 2}O{sub 5} being the principle crystalline precipitates.« less

Holographic microscopy studies of emulsions

NASA Technical Reports Server (NTRS)

Witherow, W. K.

1981-01-01

A holographic microscopy system that records and observes the dynamic properties of separation of dispersed immiscible fluids is described. The holographic construction system and reconstruction system that were used to obtain particle size and distribution information from the holograms are discussed. The holographic microscopy system is used to observed the phase separating processes in immiscible fluids that were isothermally cooled into the two phase region. Nucleation, growth rates, coalescence, and particle motion are successfully demonstrated with this system. Thus a holographic particle sizing system with a resolution of 2 micrometers and a field of view of 100 cu cm was developed that provides the capability of testing the theories of separating immiscible fluids for particle number densities in the range of 10 to 10 to the 7th power particles.

The chiral separation of triazole pesticides enantiomers by amylose-tris (3,5-dimethylphenylcarbamate) chiral stationary phase.

PubMed

Wang, Peng; Liu, Donghui; Jiang, Shuren; Xu, Yangguang; Zhou, Zhiqiang

2008-10-01

The amylose-tris(3,5-dimethylphenylcarbamate) chiral stationary phase was synthesized and used to separate the enantiomers of triazole pesticides by high-performance liquid chromatography. The mobile phase was n-hexane-isopropanol applying a flow rate of 1.0 mL/min. Six triazole pesticides were enantioselectively separated. Myclobutanil, paclobutrazol, tebuconazole, and uniconazole obtained complete separation with the resolution factors of 5.73, 2.99, 1.72, and 2.07, respectively, and imazalil and diniconazole obtained partial separation with the resolution factors of 0.79 and 0.77 under the optimized conditions. The effect of the content of isopropanol as well as column temperature on the separation was investigated. A circular dichroism detector was used to identify the enantiomers and determine the elution orders. The results showed the low temperature was good for the chiral separation except for diniconazole. The thermodynamic parameters calculated based on linear Van't Hoff plots showed the chiral separations were controlled by enthalpy.

Analyses of procyanidins in foods using Diol phase HPLC

USDA-ARS?s Scientific Manuscript database

Separation of procyanidins using silica-based HPLC suffered from poor resolution for higher oligomers and low sensitivity due to the fluorescence quenching effects of methylene chloride in the mobile phase. Optimization of a published Diol-phase HPLC method resulted in near baseline separation for p...

FUS Phase Separation Is Modulated by a Molecular Chaperone and Methylation of Arginine Cation-π Interactions.

PubMed

Qamar, Seema; Wang, GuoZhen; Randle, Suzanne J; Ruggeri, Francesco Simone; Varela, Juan A; Lin, Julie Qiaojin; Phillips, Emma C; Miyashita, Akinori; Williams, Declan; Ströhl, Florian; Meadows, William; Ferry, Rodylyn; Dardov, Victoria J; Tartaglia, Gian G; Farrer, Lindsay A; Kaminski Schierle, Gabriele S; Kaminski, Clemens F; Holt, Christine E; Fraser, Paul E; Schmitt-Ulms, Gerold; Klenerman, David; Knowles, Tuomas; Vendruscolo, Michele; St George-Hyslop, Peter

2018-04-19

Reversible phase separation underpins the role of FUS in ribonucleoprotein granules and other membrane-free organelles and is, in part, driven by the intrinsically disordered low-complexity (LC) domain of FUS. Here, we report that cooperative cation-π interactions between tyrosines in the LC domain and arginines in structured C-terminal domains also contribute to phase separation. These interactions are modulated by post-translational arginine methylation, wherein arginine hypomethylation strongly promotes phase separation and gelation. Indeed, significant hypomethylation, which occurs in FUS-associated frontotemporal lobar degeneration (FTLD), induces FUS condensation into stable intermolecular β-sheet-rich hydrogels that disrupt RNP granule function and impair new protein synthesis in neuron terminals. We show that transportin acts as a physiological molecular chaperone of FUS in neuron terminals, reducing phase separation and gelation of methylated and hypomethylated FUS and rescuing protein synthesis. These results demonstrate how FUS condensation is physiologically regulated and how perturbations in these mechanisms can lead to disease. Copyright © 2018 The Authors. Published by Elsevier Inc. All rights reserved.

Separation of polyethylene glycols and amino-terminated polyethylene glycols by high-performance liquid chromatography under near critical conditions.

PubMed

Wei, Y-Z; Zhuo, R-X; Jiang, X-L

2016-05-20

The separation and characterization of polyethylene glycols (PEGs) and amino-substituted derivatives on common silica-based reversed-phase packing columns using isocratic elution is described. This separation is achieved by liquid chromatography under the near critical conditions (LCCC), based on the number of amino functional end groups without obvious effect of molar mass for PEGs. The mobile phase is acetonitrile in water with an optimal ammonium acetate buffer. The separation mechanism of PEG and amino-substituted PEG under the near LCCC on silica-based packing columns is confirmed to be ion-exchange interaction. Under the LCCC of PEG backbone, with fine tune of buffer concentration, the retention factor ratios for benzylamine and phenol in buffered mobile phases, α(benzylamine/phenol)-values, were used to assess the ion-exchange capacity on silica-based reversed-phase packing columns. To the best of our knowledge, this is the first report on separation of amino-functional PEGs independent of the molar mass by isocratic elution using common C18 or phenyl reversed-phase packing columns. Copyright © 2016 Elsevier B.V. All rights reserved.

Effects of ammonium sulfate and sodium chloride concentration on PEG/protein liquid-liquid phase separation.

PubMed

Dumetz, André C; Lewus, Rachael A; Lenhoff, Abraham M; Kaler, Eric W

2008-09-16

When added to protein solutions, poly(ethylene glycol) (PEG) creates an effective attraction between protein molecules due to depletion forces. This effect has been widely used to crystallize proteins, and PEG is among the most successful crystallization agents in current use. However, PEG is almost always used in combination with a salt at either low or relatively high concentrations. Here the effects of sodium chloride and ammonium sulfate concentration on PEG 8000/ovalbumin liquid-liquid (L-L) phase separation are investigated. At low salt the L-L phase separation occurs at decreasing protein concentration with increasing salt concentration, presumably due to repulsive electrostatic interactions between proteins. At high salt concentration, the behavior depends on the nature of the salt. Sodium chloride has little effect on the L-L phase separation, but ammonium sulfate decreases the protein concentration at which the L-L phase separation occurs. This trend is attributed to the effects of critical fluctuations on depletion forces. The implications of these results for designing solution conditions optimal for protein crystallization are discussed.

Process Intensification of Enzymatic Fatty Acid Butyl Ester Synthesis Using a Continuous Centrifugal Contactor Separator.

PubMed

Ilmi, Miftahul; Abduh, Muhammad Y; Hommes, Arne; Winkelman, Jozef G M; Hidayat, Chusnul; Heeres, Hero J

2018-01-17

Fatty acid butyl esters were synthesized from sunflower oil with 1-butanol using a homogeneous Rhizomucor miehei lipase in a biphasic organic (triglyceride, 1-butanol, hexane)- water (with enzyme) system in a continuous setup consisting of a cascade of a stirred tank reactor and a continuous centrifugal contactor separator (CCCS), the latter being used for integrated reaction and liquid-liquid separation. A fatty acid butyl ester yield up to 93% was obtained in the cascade when operated in a once-through mode. The cascade was run for 8 h without operational issues. Enzyme recycling was studied by reintroduction of the water phase from the CCCS outlet to the stirred tank reactor. Product yield decreased over time to an average of 50% of the initial value, likely due to accumulation of 1-butanol in water phase, loss of enzyme due to agglomeration, and the formation of a separate enzyme layer.

Glycolipid class profiling by packed-column subcritical fluid chromatography.

PubMed

Deschamps, Frantz S; Lesellier, Eric; Bleton, Jean; Baillet, Arlette; Tchapla, Alain; Chaminade, Pierre

2004-06-18

The potential of packed-column subcritical fluid chromatography (SubFC) for the separation of lipid classes has been assessed in this study. Three polar stationary phases were checked: silica, diol, and poly(vinyl alcohol). Carbon dioxide (CO2) with methanol as modifier was used as mobile phase and detection performed by evaporative light scattering detection. The influence of methanol content, temperature, and pressure on the chromatographic behavior of sphingolipids and glycolipids were investigated. A complete separation of lipid classes from a crude wheat lipid extract was achieved using a modifier gradient from 10 to 40% methanol in carbon dioxide. Solute selectivity was improved using coupled silica and diol columns in series. Because the variation of eluotropic strength depending on the fluid density changes, a normalized separation factor product (NSP) was used to select the nature, the number and the order of the columns to reach the optimum glycolipid separation.

Process Intensification of Enzymatic Fatty Acid Butyl Ester Synthesis Using a Continuous Centrifugal Contactor Separator

PubMed Central

2017-01-01

Fatty acid butyl esters were synthesized from sunflower oil with 1-butanol using a homogeneous Rhizomucor miehei lipase in a biphasic organic (triglyceride, 1-butanol, hexane)– water (with enzyme) system in a continuous setup consisting of a cascade of a stirred tank reactor and a continuous centrifugal contactor separator (CCCS), the latter being used for integrated reaction and liquid–liquid separation. A fatty acid butyl ester yield up to 93% was obtained in the cascade when operated in a once-through mode. The cascade was run for 8 h without operational issues. Enzyme recycling was studied by reintroduction of the water phase from the CCCS outlet to the stirred tank reactor. Product yield decreased over time to an average of 50% of the initial value, likely due to accumulation of 1-butanol in water phase, loss of enzyme due to agglomeration, and the formation of a separate enzyme layer. PMID:29398779

Dynamics of excimer laser ablation of thin tungsten films studied by fast photography

NASA Astrophysics Data System (ADS)

Toth, Zsolt; Hopp, Bela; Kantor, Zoltan; Ignacz, Ferenc; Szoerenyi, Tamas; Bor, Zsolt

1994-09-01

The time evolution of ablation and material transport during ArF excimer laser induced blow off of tungsten films from glass substrates is studied by fast photography using delayed dye laser pulses. The analysis of experimental results combined with heat flow calculations provides evidence that tungsten removal in the solid phase is the dominant mechanism in the 40 - 200 mJ/cm2 fluence domain, while partially inhomogeneous melting is observed between 200 and 800 mJ/cm2. In this fluence range, solid fragments and a halo consisting of molten droplets are observed indicating spatial separation of the two phases. The molten phase advances faster, forming a protective mist in front of the solid piece(s). At yet higher fluences (800 - 1000 mJ/cm2), a well separated solid phase could be recorded under the halo although model calculations suggest full vaporization of the layer. This unexpected phenomenon is explained by the optical shielding effect of the halo.

Impact of x-Linkable Polymer Blends on Phase Morphology and Adhesion

NASA Astrophysics Data System (ADS)

Liu, Chun; Wan, Grace; Keene, Ellen; Harris, Joseph; Zhang, Sipei; Anderson, Stephanie; Li Pi Shan, Colin

Adhesion to dissimilar substrate is highly important to multiple industrial applications such as automotive adhesives, food packaging, transportation etc. Adhesive design has to include components that are affinity to both substrates, e.g. high surface energy polar and low surface non-polar substrates. Typically, these adhesive components are thermodynamically incompatible with each other, leading to macrophase separation and thus adhesive failure. By using functional adhesive components plus some additives, the adhesive can be in-situ cross-linked to prevent the macrophase separation with controlled phase morphology. Herein, we present the study on a cross-linkable adhesive formulation consisting of acrylic emulsion and polyolefin aqueous dispersion with additives for enhancing cross-linking and controlled phase morphologies. Contact angle measurement and ATR-IR spectroscopy are used to characterize the properties of adhesive surface. DMA is used to study the mechanical property of adhesive before and after cross-linking. The detailed phase morphologies are revealed by AFM, SEM and TEM. The resulting adhesive morphologies are correlated with the adhesive performance to establish structure-property relationship.

A new acetonitrile-free mobile phase method for LC-ELSD quantification of fructooligosaccharides in onion (Allium cepa L.).

PubMed

Downes, Katherine; Terry, Leon A

2010-06-30

Onion soluble non-structural carbohydrates consist of fructose, glucose and sucrose plus fructooligosaccharides (FOS) with degrees of polymerisation (DP) in the range of 3-19. In onion, sugars and FOS are typically separated using liquid chromatography (LC) with acetonitrile (ACN) as a mobile phase. In recent times, however, the production of ACN has diminished due, in part, to the current worldwide economic recession. A study was therefore undertaken, to find an alternative LC method to quantify sugars and FOS from onion without the need for ACN. Two mobile phases were compared; the first taken from a paper by Vågen and Slimestad (2008) using ACN mobile phase, the second, a newly reported method using ethanol (EtOH). The EtOH mobile phase eluted similar concentrations of all FOS compared to the ACN mobile phase. In addition, limit of detection, limit of quantification and relative standard deviation values were sufficiently and consistently lower for all FOS using the EtOH mobile phase. The drawback of the EtOH mobile phase was mainly the inability to separate all individual sugar peaks, yet FOS could be successfully separated. However, using the same onion extract, a previously established LC method based on an isocratic water mobile phase could be used in a second run to separate sugars. Although the ACN mobile phase method is more convenient, in the current economic climate a method based on inexpensive and plentiful ethanol is a valid alternative and could potentially be applied to other fresh produce types. In addition to the mobile phase solvent, the effect of extraction solvents on sugar and FOS concentration was also investigated. EtOH is still widely used to extract sugars from onion although previous literature has concluded that MeOH is a superior solvent. For this reason, an EtOH-based extraction method was compared with a MeOH-based method to extract both sugars and FOS. The MeOH-based extraction method was more efficacious at extracting sugars and FOS from onion flesh, eluting significantly higher concentrations of glucose, kestose, nystose and DP5-DP8. Copyright 2010 Elsevier B.V. All rights reserved.

TES buffer-induced phase separation of aqueous solutions of several water-miscible organic solvents at 298.15 K: phase diagrams and molecular dynamic simulations.

PubMed

Taha, Mohamed; Lee, Ming-Jer

2013-06-28

Water and the organic solvents tetrahydrofuran, 1,3-dioxolane, 1,4-dioxane, 1-propanol, 2-propanol, tert-butanol, acetonitrile, or acetone are completely miscible in all proportions at room temperature. Here, we present new buffering-out phase separation systems that the above mentioned organic aqueous solutions can be induced to form two liquid phases in the presence of a biological buffer 2-[[1,3-dihydroxy-2-(hydroxymethyl)propan-2-yl]amino]ethanesulfonic acid (TES). The lower liquid phase is rich in water and buffer, and the upper phase is organic rich. This observation has both practical and mechanistic interests. The phase diagrams of these systems were constructed by experimental measurements at ambient conditions. Molecular dynamic (MD) simulations were performed for TES + water + THF system to understand the interactions between TES, water, and organic solvent at molecular level. Several composition-sets for this system, beyond and inside the liquid-liquid phase-splitting region, have been simulated. Interestingly, the MD simulation for compositions inside the phase separation region showed that THF molecules are forced out from the water network to start forming a new liquid phase. The hydrogen-bonds, hydrogen-bonds lifetimes, hydrogen-bond energies, radial distribution functions, coordination numbers, the electrostatic interactions, and the van der Waals interactions between the different pairs have been calculated. Additionally, MD simulations for TES + water + tert-butanol∕acetonitrile∕acetone phase separation systems were simulated. The results from MD simulations provide an explanation for the buffering-out phenomena observed in [TES + water + organic solvent] systems by a mechanism controlled by the competitive interactions of the buffer and the organic solvent with water. The molecular mechanism reported here is helpful for designing new benign separation materials.

Advances in organic polymer-based monolithic column technology for high-resolution liquid chromatography-mass spectrometry profiling of antibodies, intact proteins, oligonucleotides, and peptides.

PubMed

Eeltink, Sebastiaan; Wouters, Sam; Dores-Sousa, José Luís; Svec, Frantisek

2017-05-19

This review focuses on the preparation of organic polymer-based monolithic stationary phases and their application in the separation of biomolecules, including antibodies, intact proteins and protein isoforms, oligonucleotides, and protein digests. Column and material properties, and the optimization of the macropore structure towards kinetic performance are also discussed. State-of-the-art liquid chromatography-mass spectrometry biomolecule separations are reviewed and practical aspects such as ion-pairing agent selection and carryover are presented. Finally, advances in comprehensive two-dimensional LC separations using monolithic columns, in particular ion-exchange×reversed-phase and reversed-phase×reversed-phase LC separations conducted at high and low pH, are shown. Copyright © 2017 Elsevier B.V. All rights reserved.

Recent progress of chiral stationary phases for separation of enantiomers in gas chromatography.

PubMed

Xie, Sheng-Ming; Yuan, Li-Ming

2017-01-01

Chromatography techniques based on chiral stationary phases are widely used for the separation of enantiomers. In particular, gas chromatography has developed rapidly in recent years due to its merits such as fast analysis speed, lower consumption of stationary phases and analytes, higher column efficiency, making it a better choice for chiral separation in diverse industries. This article summarizes recent progress of novel chiral stationary phases based on cyclofructan derivatives and chiral porous materials including chiral metal-organic frameworks, chiral porous organic frameworks, chiral inorganic mesoporous materials, and chiral porous organic cages in gas chromatography, covering original research papers published since 2010. The chiral recognition properties and mechanisms of separation toward enantiomers are also introduced. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Melt Extrusion of High-Dose Co-Amorphous Drug-Drug Combinations : Theme: Formulation and Manufacturing of Solid Dosage Forms Guest Editors: Tony Zhou and Tonglei Li.

PubMed

Arnfast, Lærke; Kamruzzaman, Md; Löbmann, Korbinian; Aho, Johanna; Baldursdottir, Stefania; Rades, Thomas; Rantanen, Jukka

2017-12-01

Many future drug products will be based on innovative manufacturing solutions, which will increase the need for a thorough understanding of the interplay between drug material properties and processability. In this study, hot melt extrusion of a drug-drug mixture with minimal amount of polymeric excipient was investigated. Using indomethacin-cimetidine as a model drug-drug system, processability of physical mixtures with and without 5% (w/w) of polyethylene oxide (PEO) were studied using Differential Scanning Calorimetry (DSC) and Small Amplitude Oscillatory Shear (SAOS) rheometry. Extrudates containing a co-amorphous glass solution were produced and the solid-state composition of these was studied with DSC. Rheological analysis indicated that the studied systems display viscosities higher than expected for small molecule melts and addition of PEO decreased the viscosity of the melt. Extrudates of indomethacin-cimetidine alone displayed amorphous-amorphous phase separation after 4 weeks of storage, whereas no phase separation was observed during the 16 week storage of the indomethacin-cimetidine extrudates containing 5% (w/w) PEO. Melt extrusion of co-amorphous extrudates with low amounts of polymer was found to be a feasible manufacturing technique. Addition of 5% (w/w) polymer reduced melt viscosity and prevented phase separation.

Nanocomposites for ultra high density information storage, devices including the same, and methods of making the same

DOEpatents

Goyal, Amit; Shin, Junsoo

2014-04-01

A nanocomposite article that includes a single-crystal or single-crystal-like substrate and heteroepitaxial, phase-separated layer supported by a surface of the substrate and a method of making the same are described. The heteroepitaxial layer can include a continuous, non-magnetic, crystalline, matrix phase, and an ordered, magnetic magnetic phase disposed within the matrix phase. The ordered magnetic phase can include a plurality of self-assembled crystalline nanostructures of a magnetic material. The phase-separated layer and the single crystal substrate can be separated by a buffer layer. An electronic storage device that includes a read-write head and a nanocomposite article with a data storage density of 0.75 Tb/in.sup.2 is also described.

Apker Award Recipient: Renormalization-Group Study of Helium Mixtures Immersed in a Porous Medium

NASA Astrophysics Data System (ADS)

Lopatnikova, Anna

1998-03-01

Superfluidity and phase separation in ^3He-^4He mixtures immersed in aerogel are studied by renormalization-group theory. Firstly, the theory is applied to jungle-gym (non-random) aerogel.(A. Lopatnikova and A.N. Berker, Phys. Rev. B 55, 3798 (1997).) This calculation is conducted via the coupled renormalization-group mappings of interactions near and away from aerogel. Superfluidity at very low ^4He concentrations and a depressed tricritical temperature are found at the onset of superfludity. A superfluid-superfluid phase separation, terminating at an isolated critical point, is found entirely within the superfluid phase. Secondly, the theory is applied to true aerogel, which has quenched disorder at both atomic and geometric levels.(A. Lopatnikova and A.N. Berker, Phys. Rev. B 56, 11865 (1997).) This calculation is conducted via the coupled renormalization-group mappings, near and away from aerogel, of quenched probability distributions of random interactions. Random-bond effects on superfluidity onset and random-field effects on superfluid phase separation are seen. The quenched randomness causes the λ line of second-order phase transitions of superfluidity onset to reach zero temperature, in agreement with general prediction and experiments. Based on these studies, the experimentally observed(S.B. Kim, J. Ma, and M.H.W. Chan, Phys. Rev. Lett. 71, 2268 (1993); N. Mulders and M.H.W. Chan, Phys. Rev. Lett. 75, 3705 (1995).) distinctive characteristics of ^3He-^4He mixtures in aerogel are related to the aerogel properties of connectivity, tenuousness, and atomic and geometric randomness.

Ordered mesoporous silica functionalized with β-cyclodextrin derivative for stereoisomer separation of flavanones and flavanone glycosides by nano-liquid chromatography and capillary electrochromatography.

PubMed

Silva, Mariana; Pérez-Quintanilla, Damián; Morante-Zarcero, Sonia; Sierra, Isabel; Marina, María Luisa; Aturki, Zeineb; Fanali, Salvatore

2017-03-24

In this paper a chiral stationary phase (CSP) was prepared by the immobilization of a β-CD derivative (3,5-dimethylphenylcarbamoylated β-CD) onto the surface of amino-functionalized spherical ordered mesoporous silica (denoted as SM) via a urea linkage using the Staudinger reaction. The CSP was packed into fused silica capillaries 100μm I.D. and evaluated by means of nano-liquid chromatography (nano-LC) and capillary electrochromatography (CEC) using model compounds for the enantio- and the diastereomeric separation. The compounds flavanone, 2'-hydroxyflavanone, 4'-hydroxyflavanone, 6-hydroxyflavanone, 4'-methoxyflavanone, 7-methoxyflavanone, hesperetin, hesperidin, naringenin, and naringin were studied using reversed and polar organic elution modes. Baseline stereoisomer resolution and good results in terms of peak efficiency and short analysis time of all studied flavonoids and flavanones glycosides were achieved in reversed phase mode, using as mobile phase a mixture of MeOH/H 2 O, 10mM ammonium acetate pH 4.5 at different ratios. For the polar organic mode using 100% of MeOH as mobile phase, the CSP showed better performances and the baseline chiral separation of several studied compounds occurred in an analysis time of less than 10min. Good results were also achieved by CEC employing two different mobile phases. The use of MeOH/H 2 O, 5mM ammonium acetate buffer pH 6.0 (90/10, v/v) was very effective for the chiral resolution of flavanone and its methoxy and hydroxy derivatives. Copyright © 2017 Elsevier B.V. All rights reserved.

Phase partitioning in space and on earth

NASA Technical Reports Server (NTRS)

Van Alstine, James M.; Karr, Laurel J.; Snyder, Robert S.; Matsos, Helen C.; Curreri, Peter A.; Harris, J. Milton; Bamberger, Stephan B.; Boyce, John; Brooks, Donald E.

1987-01-01

The influence of gravity on the efficiency and quality of the impressive separations achievable by bioparticle partitioning is investigated by demixing polymer phase systems in microgravity. The study involves the neutral polymers dextran and polyethylene glycol, which form a two-phase system in aqueous solution at low concentrations. It is found that demixing in low-gravity occurs primarily by coalescence, whereas on earth the demixing occurs because of density differences between the phases.

URANIUM SEPARATION PROCESS

DOEpatents

McVey, W.H.; Reas, W.H.

1959-03-10

The separation of uranium from an aqueous solution containing a water soluble uranyl salt is described. The process involves adding an alkali thiocyanate to the aqueous solution, contacting the resulting solution with methyl isobutyl ketons and separating the resulting aqueous and organic phase. The uranium is extracted in the organic phase as UO/sub 2/(SCN)/sub/.

Accelerating the sludge disintegration potential of a novel bacterial strain Planococcus jake 01 by CaCl2 induced deflocculation.

PubMed

Kavitha, S; Saranya, T; Kaliappan, S; Adish Kumar, S; Yeom, Ick Tae; Rajesh Banu, J

2015-01-01

The present study investigates the impacts of phase separated disintegration through CaCl2 (calcium chloride) mediated biosurfactant producing bacterial pretreatment. In the initial phase of the study, the flocs were disintegrated (deflocculation) with 0.06g/gSS of CaCl2. In the subsequent phase, the sludge biomass was disintegrated (cell disintegration) through potent biosurfactant producing new novel bacteria, Planococcus jake 01. The pretreatment showed that suspended solids reduction and chemical oxygen demand solubilization for deflocculated - bacterially pretreated sludge was found to be 17.14% and 14.14% which were comparatively higher than flocculated sludge (treated with bacteria alone). The biogas yield potential of deflocculated - bacterially pretreated, flocculated, and control sludges were observed to be 0.322(L/gVS), 0.225(L/gVS) and 0.145(L/gVS) respectively. To our knowledge, this is the first study to present the thorough knowledge of biogas production potential through a novel phase separated biosurfactant bacterial pretreatment. Copyright © 2014 Elsevier Ltd. All rights reserved.

Combination of Complex-Based and Magnitude-Based Multiecho Water-Fat Separation for Accurate Quantification of Fat-Fraction

PubMed Central

Yu, Huanzhou; Shimakawa, Ann; Hines, Catherine D. G.; McKenzie, Charles A.; Hamilton, Gavin; Sirlin, Claude B.; Brittain, Jean H.; Reeder, Scott B.

2011-01-01

Multipoint water–fat separation techniques rely on different water–fat phase shifts generated at multiple echo times to decompose water and fat. Therefore, these methods require complex source images and allow unambiguous separation of water and fat signals. However, complex-based water–fat separation methods are sensitive to phase errors in the source images, which may lead to clinically important errors. An alternative approach to quantify fat is through “magnitude-based” methods that acquire multiecho magnitude images. Magnitude-based methods are insensitive to phase errors, but cannot estimate fat-fraction greater than 50%. In this work, we introduce a water–fat separation approach that combines the strengths of both complex and magnitude reconstruction algorithms. A magnitude-based reconstruction is applied after complex-based water–fat separation to removes the effect of phase errors. The results from the two reconstructions are then combined. We demonstrate that using this hybrid method, 0–100% fat-fraction can be estimated with improved accuracy at low fat-fractions. PMID:21695724

Morphological Simulation of Phase Separation Coupled Oscillation Shear and Varying Temperature Fields

NASA Astrophysics Data System (ADS)

Wang, Heping; Li, Xiaoguang; Lin, Kejun; Geng, Xingguo

2018-05-01

This paper explores the effect of the shear frequency and Prandtl number ( Pr) on the procedure and pattern formation of phase separation in symmetric and asymmetric systems. For the symmetric system, the periodic shear significantly prolongs the spinodal decomposition stage and enlarges the separated domain in domain growth stage. By adjusting the Pr and shear frequency, the number and orientation of separated steady layer structures can be controlled during domain stretch stage. The numerical results indicate that the increase in Pr and decrease in the shear frequency can significantly increase in the layer number of the lamellar structure, which relates to the decrease in domain size. Furthermore, the lamellar orientation parallel to the shear direction is altered into that perpendicular to the shear direction by further increasing the shear frequency, and also similar results for larger systems. For asymmetric system, the quantitative analysis shows that the decrease in the shear frequency enlarges the size of separated minority phases. These numerical results provide guidance for setting the optimum condition for the phase separation under periodic shear and slow cooling.

The Two-Phase Flow Separator Experiment Breadboard Model: Reduced Gravity Aircraft Results

NASA Technical Reports Server (NTRS)

Rame, E; Sharp, L. M.; Chahine, G.; Kamotani, Y.; Gotti, D.; Owens, J.; Gilkey, K.; Pham, N.

2015-01-01

Life support systems in space depend on the ability to effectively separate gas from liquid. Passive cyclonic phase separators use the centripetal acceleration of a rotating gas-liquid mixture to carry out phase separation. The gas migrates to the center, while gas-free liquid may be withdrawn from one of the end plates. We have designed, constructed and tested a breadboard that accommodates the test sections of two independent principal investigators and satisfies their respective requirements, including flow rates, pressure and video diagnostics. The breadboard was flown in the NASA low-gravity airplane in order to test the system performance and design under reduced gravity conditions.

Polymer Dispersed Liquid Crystal Displays

NASA Astrophysics Data System (ADS)

Doane, J. William

The following sections are included: * INTRODUCTION AND HISTORICAL DEVELOPMENT * PDLC MATERIALS PREPARATION * Polymerization induced phase separation (PIPS) * Thermally induced phase separation (TIPS) * Solvent induced phase separation (SIPS) * Encapsulation (NCAP) * RESPONSE VOLTAGE * Dielectric and resistive effects * Radial configuration * Bipolar configuration * Other director configurations * RESPONSE TIME * DISPLAY CONTRAST * Light scattering and index matching * Incorporation of dyes * Contrast measurements * PDLC DISPLAY DEVICES AND INNOVATIONS * Reflective direct view displays * Large-scale, flexible displays * Switchable windows * Projection displays * High definition spatial light modulator * Haze-free PDLC shutters: wide angle view displays * ENVIRONMENTAL STABILITY * ACKNOWLEDGEMENTS * REFERENCES

Separation of VX, RVX and GB Enantiomers Using Liquid ChromatographyTime-of-Flight Mass Spectrometry

DTIC Science & Technology

2016-02-01

Torrance, CA). The mobile phase consisted of n - hexane (A) and isopropyl alcohol (B), and sample volume was 10 µL. Separation was achieved using...level for preparative separation. All reagents and solvents were high-performance LC grade. Hexane and isopropyl alcohol were purchased from Fisher...1 column and normal-phase LC were used with a mobile phase of 96/4 (v/v %) hexane /isopropyl alcohol at a flow rate of 0.6 mL/min. The enantiomers

Gas-liquid chromatography with a volatile "stationary" liquid phase.

PubMed

Wells, P S; Zhou, S; Parcher, J F

2002-05-01

A unique type of gas-liquid chromatography is described in which both mobile and "stationary" phases are composed of synthetic mixtures of helium and carbon dioxide. At temperatures below the critical point of the binary mixture and pressures above the vapor pressure of pure liquid carbon dioxide, helium and carbon dioxide can form two immiscible phases over extended composition ranges. A binary vapor phase enriched in helium can act as the mobile phase for chromatographic separations, whereas a CO2-rich liquid in equilibrium with the vapor phase, but condensed on the column wall, can act as a pseudostationary phase. Several examples of chromatographic separations obtained in "empty" capillary columns with no ordinary stationary liquid phase illustrate the range of conditions that produce such separations. In addition, several experiments are reported that confirm the proposed two-phase hypothesis. The possible consequences of the observed chromatographic phenomenon in the field of supercritical fluid chromatography with helium headspace carbon dioxide are discussed.

Phase diagram of a symmetric electron-hole bilayer system: a variational Monte Carlo study.

PubMed

Sharma, Rajesh O; Saini, L K; Bahuguna, Bhagwati Prasad

2018-05-10

We study the phase diagram of a symmetric electron-hole bilayer system at absolute zero temperature and in zero magnetic field within the quantum Monte Carlo approach. In particular, we conduct variational Monte Carlo simulations for various phases, i.e. the paramagnetic fluid phase, the ferromagnetic fluid phase, the anti-ferromagnetic Wigner crystal phase, the ferromagnetic Wigner crystal phase and the excitonic phase, to estimate the ground-state energy at different values of in-layer density and inter-layer spacing. Slater-Jastrow style trial wave functions, with single-particle orbitals appropriate for different phases, are used to construct the phase diagram in the (r s , d) plane by finding the relative stability of trial wave functions. At very small layer separations, we find that the fluid phases are stable, with the paramagnetic fluid phase being particularly stable at [Formula: see text] and the ferromagnetic fluid phase being particularly stable at [Formula: see text]. As the layer spacing increases, we first find that there is a phase transition from the ferromagnetic fluid phase to the ferromagnetic Wigner crystal phase when d reaches 0.4 a.u. at r s   =  20, and before there is a return to the ferromagnetic fluid phase when d approaches 1 a.u. However, for r s   <  20 and [Formula: see text] a.u., the excitonic phase is found to be stable. We do not find that the anti-ferromagnetic Wigner crystal is stable over the considered range of r s and d. We also find that as r s increases, the critical layer separations for Wigner crystallization increase.

Use of vancomycin silica stationary phase in packed capillary electrochromatography I. Enantiomer separation of basic compounds.

PubMed

Desiderio, C; Aturki, Z; Fanali, S

2001-02-01

Chiral separation of basic compounds was achieved by using 75 or 100 microm ID fused-silica capillaries packed with a vanoomycin-modified diol silica stationary phase. The capillary was firstly packed for about 12 cm with a slurry mixture composed of diolsilica (3:1) then with the vancomycin modified diol-silica (3:1) (23 cm), and finally with diol-silica (3:1) for about 2 cm. Frits were prepared by a heating wire at the two ends of the capillary; the detector window was prepared at 8.5 cm from the end of the capillary where vancomycin was not present. The influence of the mobile phase composition (pH and concentration, organic modifier type and concentration) on the velocity of the electroosmotic flow, chiral resolution and enantioselectivity was studied. Good enantiomeric resolution was achieved for atenolol, oxprenolol, propranolol, and venlafaxine using a mobile phase composition of 100 mM ammonium acetate solution (pH 6)/water/acetonitrile (5:5:90 v/v/v) while for terbutaline a mixture of 5:15:80 v/v/v provided the best separations. The use of methanol instead of acetonitrile caused a general increase of enantiomer resolution of the studied compounds together with a reduction of efficiency and detector response. However, the combination of acetonitrile and methanol in the mobile phase (as, e.g., 10% methanol and 80% acetonitrile) allowed to improve the enantiomer resolution with satisfactory detector response.

The Chemistry of Separations Ligand Degradation by Organic Radical Cations

DOE PAGES

Mezyk, Stephen P.; Horne, Gregory P.; Mincher, Bruce J.; ...

2016-12-01

Solvent based extractions of used nuclear fuel use designer ligands in an organic phase extracting ligand complexed metal ions from an acidic aqueous phase. These extractions will be performed in highly radioactive environments, and the radiation chemistry of all these complexants and their diluents will play a major role in determining extraction efficiency, separation factors, and solvent-recycle longevity. Although there has been considerable effort in investigating ligand damage occurring in acidic water radiolysis conditions, only minimal fundamental kinetic and mechanistic data has been reported for the degradation of extraction ligands in the organic phase. Extraction solvent phases typically use normalmore » alkanes such as dodecane, TPH, and kerosene as diluents. The radiolysis of such diluents produce a mixture of radical cations (R •+), carbon-centered radicals (R •), solvated electrons, and molecular products such as hydrogen. Typically, the radical species will preferentially react with the dissolved oxygen present to produce relatively inert peroxyl radicals. This isolates the alkane radical cation species, R •+ as the major radiolytically-induced organic species that can react with, and degrade, extraction agents in this phase. Here we report on our recent studies of organic radical cation reactions with various ligands. Elucidating these parameters, and combining them with the known acidic aqueous phase chemistry, will allow a full, fundamental, understanding of the impact of radiation on solvent extraction based separation processes to be achieved.« less

Dehydration induced phase transitions in a microfluidic droplet array for the separation of biomolecules

NASA Astrophysics Data System (ADS)

Nelson, Chris; Anna, Shelley

2013-11-01

Droplet-based strategies for fluid manipulation have seen significant application in microfluidics due to their ability to compartmentalize solutions and facilitate highly parallelized reactions. Functioning as micro-scale reaction vessels, droplets have been used to study protein crystallization, enzyme kinetics, and to encapsulate whole cells. Recently, the mass transport out of droplets has been used to concentrate solutions and induce phase transitions. Here, we show that droplets trapped in a microfluidic array will spontaneously dehydrate over the course of several hours. By loading these devices with an initially dilute aqueous polymer solution, we use this slow dehydration to observe phase transitions and the evolution of droplet morphology in hundreds of droplets simultaneously. As an example, we trap and dehydrate droplets of a model aqueous two-phase system consisting of polyethylene glycol and dextran. Initially the drops are homogenous, then after some time the polymer concentration reaches a critical point and two phases form. As water continues to leave the system, the drops transition from a microemulsion of DEX in PEG to a core-shell configuration. Eventually, changes in interfacial tension, driven by dehydration, cause the DEX core to completely de-wet from the PEG shell. Since aqueous two phase systems are able to selectively separate a variety of biomolecules, this core shedding behavior has the potential to provide selective, on-chip separation and concentration.

The Chemistry of Separations Ligand Degradation by Organic Radical Cations

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

Mezyk, Stephen P.; Horne, Gregory P.; Mincher, Bruce J.

Solvent based extractions of used nuclear fuel use designer ligands in an organic phase extracting ligand complexed metal ions from an acidic aqueous phase. These extractions will be performed in highly radioactive environments, and the radiation chemistry of all these complexants and their diluents will play a major role in determining extraction efficiency, separation factors, and solvent-recycle longevity. Although there has been considerable effort in investigating ligand damage occurring in acidic water radiolysis conditions, only minimal fundamental kinetic and mechanistic data has been reported for the degradation of extraction ligands in the organic phase. Extraction solvent phases typically use normalmore » alkanes such as dodecane, TPH, and kerosene as diluents. The radiolysis of such diluents produce a mixture of radical cations (R •+), carbon-centered radicals (R •), solvated electrons, and molecular products such as hydrogen. Typically, the radical species will preferentially react with the dissolved oxygen present to produce relatively inert peroxyl radicals. This isolates the alkane radical cation species, R •+ as the major radiolytically-induced organic species that can react with, and degrade, extraction agents in this phase. Here we report on our recent studies of organic radical cation reactions with various ligands. Elucidating these parameters, and combining them with the known acidic aqueous phase chemistry, will allow a full, fundamental, understanding of the impact of radiation on solvent extraction based separation processes to be achieved.« less

CEC with new monolithic stationary phase based on a fluorinated monomer, trifluoroethyl methacrylate.

PubMed

Yurtsever, Arda; Saraçoğlu, Berna; Tuncel, Ali

2009-02-01

A new, fluorinated monolithic stationary phase for CEC was first synthesized by a single-stage, thermally initiated copolymerization of a fluorinated monomer, 2,2,2-trifluoroethyl methacrylate (TFEM) and ethylene dimethacrylate (EDMA) in the presence of a porogen mixture. In this preparation, 2-acrylamido-2-methyl-1-propanesulfonic acid was used as the charge-bearing monomer. The porogen mixture was prepared by mixing isoamylalcohol and 1,4-butanediol. A clear increase in the electroosmotic mobility was observed with increasing pH. The electroosmotic mobility decreased with increasing ACN concentration. Poly(TFEM-co-EDMA) monolith prepared under optimized polymerization conditions was successfully used in the separation of alkylbenzenes and phenols by CEC. The best chromatographic separation for alkylbenzenes was performed with lower ACN concentrations (i.e. 60% v/v) with respect to the common acrylic-based CEC monoliths. The theoretical plate numbers up to 220 000 plates/m were achieved in the reversed phase separation of phenols. Poly(TFEM-co-EDMA) monolith also allowed the simultaneous separation of aniline and benzoic acid derivatives by a single run and by using a lower ACN concentration in the mobile phase with respect to the similar electrochromatographic separations. A stable retention behaviour in reversed phase separation of alkylbenzenes was obtained with the poly(TFEM-co-EDMA) monolith.

A nitromethane-based HPLC system alternative to acetonitrile for carotenoid analysis of fruit and vegetables.

PubMed

Sandmann, Gerhard

2010-01-01

Acetonitrile-based HPLC systems are the most commonly used for carotenoid analysis from different plant tissues. Because of the acetonitrile shortage, an HPLC system for the separation of carotenoids on C(18) reversed-phase columns was developed in which an acetonitrile-alcohol-based mobile phase was replaced by nitromethane. This solvent comes closest to acetonitrile with respect to its elutrophic property. Our criterion was to obtain similar separation and retention times for a range of differently structured carotenoids. This was achieved by further increase in the lipophilicity with ethylacetate. For all the carotenoids which we tested, we found co-elution only of β-cryptoxanthin and lycopene. By addition of 1% of water, separation of this pair of carotenoids was also achieved. The final recommended mobile phase consisted of nitromethane : 2-propanol : ethyl acetate : water (79 : 10 : 10 : 1, by volume). On Nucleosil C(18) columns and related ones like Hypersil C(18), we obtained separation of carotenes, hydroxyl, epoxy and keto derivatives, which resembles the excellent separation properties of acetonitrile-based mobile phases on C(18) reversed phase columns. We successfully applied the newly developed HPLC system to the separation of carotenoids from different vegetables and fruit. Copyright © 2010 John Wiley & Sons, Ltd.

Synthesis of a stationary phase based on silica modified with branched octadecyl groups by Michael addition and photoinduced thiol-yne click chemistry for the separation of basic compounds.

PubMed

Huang, Guang; Ou, Junjie; Wang, Hongwei; Ji, Yongsheng; Wan, Hao; Zhang, Zhang; Peng, Xiaojun; Zou, Hanfa

2016-04-01

A novel silica-based stationary phase with branched octadecyl groups was prepared by the sequential employment of the Michael addition reaction and photoinduced thiol-yne click chemistry with 3-aminopropyl-functionalized silica microspheres as the initial material. The resulting stationary phase denoted as SiO2 -N(C18)4 was characterized by elemental analysis, FTIR spectroscopy and Raman spectroscopy, demonstrating the existence of branched octadecyl groups in silica microspheres. The separations of benzene homologous compounds, acid compounds and amine analogues were conducted, demonstrating mixed-mode separation mechanism on SiO2 -N(C18)4 . Baseline separation of basic drugs mixture was acquired with the mobile phase of acetonitrile/H2 O (5%, v/v). SiO2 -N(C18)4 was further applied to separate Corydalis yanhusuo Wang water extracts, and more baseline separation peaks were obtained for SiO2 -N(C18)4 than those on Atlantis dC18 column. It can be expected that this new silica-based stationary phase will exhibit great potential in the analysis of basic compounds. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Separation of phenolic acids from sugarcane rind by online solid-phase extraction with high-speed counter-current chromatography.

PubMed

Geng, Ping; Fang, Yingtong; Xie, Ronglong; Hu, Weilun; Xi, Xingjun; Chu, Qiao; Dong, Genlai; Shaheen, Nusrat; Wei, Yun

2017-02-01

Sugarcane rind contains some functional phenolic acids. The separation of these compounds from sugarcane rind is able to realize the integrated utilization of the crop and reduce environment pollution. In this paper, a novel protocol based on interfacing online solid-phase extraction with high-speed counter-current chromatography (HSCCC) was established, aiming at improving and simplifying the process of phenolic acids separation from sugarcane rind. The conditions of online solid-phase extraction with HSCCC involving solvent system, flow rate of mobile phase as well as saturated extent of absorption of solid-phase extraction were optimized to improve extraction efficiency and reduce separation time. The separation of phenolic acids was performed with a two-phase solvent system composed of butanol/acetic acid/water at a volume ratio of 4:1:5, and the developed online solid-phase extraction with HSCCC method was validated and successfully applied for sugarcane rind, and three phenolic acids including 6.73 mg of gallic acid, 10.85 mg of p-coumaric acid, and 2.78 mg of ferulic acid with purities of 60.2, 95.4, and 84%, respectively, were obtained from 150 mg sugarcane rind crude extracts. In addition, the three different elution methods of phenolic acids purification including HSCCC, elution-extrusion counter-current chromatography and back-extrusion counter-current chromatography were compared. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

In situ reinforced polymers using low molecular weight compounds

NASA Astrophysics Data System (ADS)

Yordem, Onur Sinan

2011-12-01

The primary objective of this research is to generate reinforcing domains in situ during the processing of polymers by using phase separation techniques. Low molecular weight compounds were mixed with polymers where the process viscosity is reduced at process temperatures and mechanical properties are improved once the material system is cooled or reacted. Thermally induced phase separation and thermotropic phase transformation of low molar mass compounds were used in isotactic polypropylene (iPP) and poly(ether ether ketone) (PEEK) resins. Reaction induced phase separation was utilized in thermosets to generate anisotropic reinforcements. A new strategy to increase fracture toughness of materials was introduced. Simultaneously, enhancement in stiffness and reduction in process viscosity were also attained. Materials with improved rheological and mechanical properties were prepared by using thermotropic phase transformations of metal soaps in polymers (calcium stearate/iPP). Morphology and thermal properties were studied using WAXS, DSC and SEM. Mechanical and rheological investigation showed significant reduction in process viscosity and substantial improvement in fracture toughness were attained. Effects of molecular architecture of metal soaps were investigated in PEEK (calcium stearate/PEEK and sodium stearate/PEEK). The selected compounds reduced the process viscosity due to the high temperature co-continuous morphology of metal soaps. Unlike the iPP system that incorporates spherical particles, interaction between PEEK and metal soaps resulted in two discrete and co-continuous phases of PEEK and the metal stearates. DMA and melt rheology exhibited that sodium stearate/PEEK composites are stiffer. Effective moduli of secondary metal stearate phase were calculated using different composite theories, which suggested bicontinuous morphology to the metal soaps in PEEK. Use of low molecular weight crystallizable solvents was investigated in reactive systems. Formation of anisotropic reinforcements was evaluated using dimethyl sulfone (DMS) as the crystallizable diluent and diglycidyl ether of bisphenol-A (DGEBA)/m-phenylene diamine (mPDA) material system as the epoxy thermoset. Miscible blends of DMS and DGEBA/mPDA form homogenous mixtures that undergo polymerization induced phase separation, once the DGEBA oligomers react with mPDA. The effect of the competition between the crystallization and phase separation of DMS resulted in nano-wires to micro-scale fiber-like crystals that were generated by adjusting the reaction temperature and DMS concentration.

H-T magnetic phase diagrams of electron-doped Sm1-xCaxMnO3: Evidence for phase separation and metamagnetic transitions

NASA Astrophysics Data System (ADS)

Respaud, M.; Broto, J. M.; Rakoto, H.; Vanacken, J.; Wagner, P.; Martin, C.; Maignan, A.; Raveau, B.

2001-04-01

The magnetic properties of the polycrystalline manganites Sm1-xCaxMnO3 have been studied for (1>=x>=2/3) under high magnetic fields up to 50 T. The phase diagrams in the H-T plane have been determined. The more representative systems have also been studied by means of neutron diffraction experiments. Increasing the electron concentration in CaMnO3 leads to an increasing minor ferromagnetic (FM) component superimposed on the antiferromagnetic (AFM) background. A cluster-glass regime is observed for x=0.9, where FM clusters are embedded in the G-type AFM matrix of the parent compound. For 0.8>=x, field-induced transitions from the AFM ground state to a FM one have been observed. They correspond to the melting of the C-type AFM orbital-ordered phase for x=0.8, and to the collapse of the charge-ordered phase for x=3/4. In between these two characteristic domains of concentration, x~0.85, the magnetization curves show a superposition of the two above behaviors, suggesting phase separation. This scenario is consistent with the neutron diffraction results showing that the crystalline and magnetic structures of each phase coexist.

Polar Aprotic Modifiers for Chromatographic Separation and Back-Exchange Reduction for Protein Hydrogen/Deuterium Exchange Monitored by Fourier Transform Ion Cyclotron Resonance Mass Spectrometry

NASA Astrophysics Data System (ADS)

Valeja, Santosh G.; Emmett, Mark R.; Marshall, Alan G.

2012-04-01

Hydrogen/deuterium exchange monitored by mass spectrometry is an important non-perturbing tool to study protein structure and protein-protein interactions. However, water in the reversed-phase liquid chromatography mobile phase leads to back-exchange of D for H during chromatographic separation of proteolytic peptides following H/D exchange, resulting in incorrect identification of fast-exchanging hydrogens as unexchanged hydrogens. Previously, fast high-performance liquid chromatography (HPLC) and supercritical fluid chromatography have been shown to decrease back-exchange. Here, we show that replacement of up to 40% of the water in the LC mobile phase by the modifiers, dimethylformamide (DMF) and N-methylpyrrolidone (NMP) (i.e., polar organic modifiers that lack rapid exchanging hydrogens), significantly reduces back-exchange. On-line LC micro-ESI FT-ICR MS resolves overlapped proteolytic peptide isotopic distributions, allowing for quantitative determination of the extent of back-exchange. The DMF modified solvent composition also improves chromatographic separation while reducing back-exchange relative to conventional solvent.

Separation-oriented derivatization of native fluorescent compounds through fluorous labeling followed by liquid chromatography with fluorous-phase.

PubMed

Sakaguchi, Yohei; Yoshida, Hideyuki; Todoroki, Kenichiro; Nohta, Hitoshi; Yamaguchi, Masatoshi

2009-06-15

We have developed a new and simple method based on "fluorous derivatization" for LC of native fluorescent compounds. This method involves the use of a column with a fluorous stationary phase. Native fluorescent analytes with target functional groups are precolumn derivatized with a nonfluorescent fluorous tag, and the fluorous-labeled analytes are retained in the column, whereas underivatized substances are not. Only the retained fluorescent analytes are detected fluorometrically at appropriate retention times, and retained substrates without fluorophores are not detected. In this study, biologically important carboxylic acids (homovanillic acid, vanillylmandelic acid, and 5-hydroxyindoleacetic acid) and drugs (naproxen, felbinac, flurbiprofen, and etodolac) were used as model native fluorescent compounds. Experimental results indicate that the fluorous-phase column can selectively retain fluorous compounds including fluorous-labeled analytes on the basis of fluorous separation. We believe that separation-oriented derivatization presented here is the first step toward the introduction of fluorous derivatization in quantitative LC analysis.

Comprehensive overview of recent preparation and application trends of various open tubular capillary columns in separation science.

PubMed

Cheong, Won Jo; Ali, Faiz; Kim, Yune Sung; Lee, Jin Wook

2013-09-20

Open tubular (OT) capillary columns have been increasingly used in a variety of fields of separation science such as CEC, LC, and SPE. Especially their application in CEC has attracted a lot of attention for their outstanding separation performance. Various forms of OT stationary phase materials have been employed such as in-situ prepared polymers, molecular imprinted polymers (MIPs), brush ligands, host ligands, block copolymers, aptamers, carbon nanotubes, polysaccharides, proteins, tentacles, nanoparticles, monoliths, and polyelectrolyte multi-layers. They have been prepared either in the chemically bound format or physically adsorbed format. Sol-gel technologies and nanoparticles have been sometimes involved in their preparation. There have been also some unique miscellaneous studies, for example, adopting preferentially adsorbed mobile phase components as stationary phases. In this review, recent progresses since mostly 2007 will be critically discussed in detail with some summarized descriptions for the work before the date. Copyright © 2013 Elsevier B.V. All rights reserved.

Phase separation like dynamics during Myxococcus xanthus fruiting body formation

NASA Astrophysics Data System (ADS)

Liu, Guannan; Thutupalli, Shashi; Wigbers, Manon; Shaevitz, Joshua

2015-03-01

Collective motion exists in many living organisms as an advantageous strategy to help the entire group with predation, forage, and survival. However, the principles of self-organization underlying such collective motions remain unclear. During various developmental stages of the soil-dwelling bacterium, Myxococcus xanthus, different types of collective motions are observed. In particular, when starved, M. xanthus cells eventually aggregate together to form 3-dimensional structures (fruiting bodies), inside which cells sporulate in response to the stress. We study the fruiting body formation process as an out of equilibrium phase separation process. As local cell density increases, the dynamics of the aggregation M. xanthus cells switch from a spatio-temporally random process, resembling nucleation and growth, to an emergent pattern formation process similar to a spinodal decomposition. By employing high-resolution microscopy and a video analysis system, we are able to track the motion of single cells within motile collective groups, while separately tuning local cell density, cell velocity and reversal frequency, probing the multi-dimensional phase space of M. xanthus development.

Efficient capture of SO2 by a binary mixture of caprolactam tetrabutyl ammonium bromide ionic liquid and water.

PubMed

Duan, Erhong; Guo, Bin; Zhang, Miaomiao; Guan, Yanan; Sun, Hua; Han, Jing

2011-10-30

The solubility of SO(2) in a binary mixture of water and caprolactam tetrabutyl ammonium bromide ionic liquid (CPL-TBAB IL) was investigated. Though the ionic liquid and water were fully miscible, a phase separation occurred when SO(2) was introduced into the mixture. The SO(2) concentrated in the lower layer, and it could be released by heating the solution under reduced pressure (382.2K, 10.1 kPa). After desorption, the mixture could be reused to absorb SO(2). It was found that SO(2) acts as a switch to cause the water and CPL-TBAB IL to phase separate, and the mechanics of this phase separation process was studied by gas chromatography-mass spectrometry, fourier transform-infrared spectroscopy and Karl-Fisher titration. The absorption and desorption of SO(2) in the CPL-TBAB/water mixtures were reversible. Copyright © 2011 Elsevier B.V. All rights reserved.

Water-fat separation with parallel imaging based on BLADE.

PubMed

Weng, Dehe; Pan, Yanli; Zhong, Xiaodong; Zhuo, Yan

2013-06-01

Uniform suppression of fat signal is desired in clinical applications. Based on phase differences introduced by different chemical shift frequencies, Dixon method and its variations are used as alternatives of fat saturation methods, which are sensitive to B0 inhomogeneities. Iterative Decomposition of water and fat with Echo Asymmetry and Least squares estimation (IDEAL) separates water and fat images with flexible echo shifting. Periodically Rotated Overlapping ParallEL Lines with Enhanced Reconstruction (PROPELLER, alternatively termed as BLADE), in conjunction with IDEAL, yields Turboprop IDEAL (TP-IDEAL) and allows for decomposition of water and fat signal with motion correction. However, the flexibility of its parameter setting is limited, and the related phase correction is complicated. To address these problems, a novel method, BLADE-Dixon, is proposed in this study. This method used the same polarity readout gradients (fly-back gradients) to acquire in-phase and opposed-phases images, which led to less complicated phase correction and more flexible parameter setting compared to TP-IDEAL. Parallel imaging and undersampling were integrated to reduce scan time. Phantom, orbit, neck and knee images were acquired with BLADE-Dixon. Water-fat separation results were compared to those measured with conventional turbo spin echo (TSE) Dixon and TSE with fat saturation, respectively, to demonstrate the performance of BLADE-Dixon. Copyright © 2013 Elsevier Inc. All rights reserved.

Pre-Combustion Carbon Dioxide Capture by a New Dual Phase Ceramic-Carbonate Membrane Reactor

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

Lin, Jerry Y. S.

2015-01-31

This report documents synthesis, characterization and carbon dioxide permeation and separation properties of a new group of ceramic-carbonate dual-phase membranes and results of a laboratory study on their application for water gas shift reaction with carbon dioxide separation. A series of ceramic-carbonate dual phase membranes with various oxygen ionic or mixed ionic and electronic conducting metal oxide materials in disk, tube, symmetric, and asymmetric geometric configurations was developed. These membranes, with the thickness of 10 μm to 1.5 mm, show CO 2 permeance in the range of 0.5-5×10 -7 mol·m -2·s -1·Pa -1 in 500-900°C and measured CO 2/N 2more » selectivity of up to 3000. CO 2 permeation mechanism and factors that affect CO 2 permeation through the dual-phase membranes have been identified. A reliable CO 2 permeation model was developed. A robust method was established for the optimization of the microstructures of ceramic-carbonate membranes. The ceramic-carbonate membranes exhibit high stability for high temperature CO 2 separations and water gas shift reaction. Water gas shift reaction in the dual-phase membrane reactors was studied by both modeling and experiments. It is found that high temperature syngas water gas shift reaction in tubular ceramic-carbonate dual phase membrane reactor is feasible even without catalyst. The membrane reactor exhibits good CO 2 permeation flux, high thermal and chemical stability and high thermal shock resistance. Reaction and separation conditions in the membrane reactor to produce hydrogen of 93% purity and CO 2 stream of >95% purity, with 90% CO 2 capture have been identified. Integration of the ceramic-carbonate dual-phase membrane reactor with IGCC process for carbon dioxide capture was analyzed. A methodology was developed to identify optimum operation conditions for a membrane tube of given dimensions that would treat coal syngas with targeted performance. The calculation results show that the dual-phase membrane reactor could improve IGCC process efficiency but the cost of the membrane reactor with membranes having current CO 2 permeance is high. Further research should be directed towards improving the performance of the membranes and developing cost-effective, scalable methods for fabrication of dual-phase membranes and membrane reactors.« less

Water outlet control mechanism for fuel cell system operation in variable gravity environments

NASA Technical Reports Server (NTRS)

Vasquez, Arturo (Inventor); McCurdy, Kerri L. (Inventor); Bradley, Karla F. (Inventor)

2007-01-01

A self-regulated water separator provides centrifugal separation of fuel cell product water from oxidant gas. The system uses the flow energy of the fuel cell's two-phase water and oxidant flow stream and a regulated ejector or other reactant circulation pump providing the two-phase fluid flow. The system further uses a means of controlling the water outlet flow rate away from the water separator that uses both the ejector's or reactant pump's supply pressure and a compressibility sensor to provide overall control of separated water flow either back to the separator or away from the separator.

Surface phase separation, dewetting feature size, and crystal morphology in thin films of polystyrene/poly(ε-caprolactone) blend.

PubMed

Ma, Meng; He, Zhoukun; Li, Yuhan; Chen, Feng; Wang, Ke; Zhang, Qing; Deng, Hua; Fu, Qiang

2012-12-01

Thin films of polystyrene (PS)/poly(ε-caprolactone) (PCL) blends were prepared by spin-coating and characterized by tapping mode force microscopy (AFM). Effects of the relative concentration of PS in polymer solution on the surface phase separation and dewetting feature size of the blend films were systematically studied. Due to the coupling of phase separation, dewetting, and crystallization of the blend films with the evaporation of solvent during spin-coating, different size of PS islands decorated with various PCL crystal structures including spherulite-like, flat-on individual lamellae, and flat-on dendritic crystal were obtained in the blend films by changing the film composition. The average distance of PS islands was shown to increase with the relative concentration of PS in casting solution. For a given ratio of PS/PCL, the feature size of PS appeared to increase linearly with the square of PS concentration while the PCL concentration only determined the crystal morphology of the blend films with no influence on the upper PS domain features. This is explained in terms of vertical phase separation and spinodal dewetting of the PS rich layer from the underlying PCL rich layer, leading to the upper PS dewetting process and the underlying PCL crystalline process to be mutually independent. Copyright © 2012 Elsevier Inc. All rights reserved.

Preparation and Characterization of Hydrophilically Modified PVDF Membranes by a Novel Nonsolvent Thermally Induced Phase Separation Method

PubMed Central

Hu, Ningen; Xiao, Tonghu; Cai, Xinhai; Ding, Lining; Fu, Yuhua; Yang, Xing

2016-01-01

In this study, a nonsolvent thermally-induced phase separation (NTIPS) method was first proposed to fabricate hydrophilically-modified poly(vinylidene fluoride) (PVDF) membranes to overcome the drawbacks of conventional thermally-induced phase separation (TIPS) and nonsolvent-induced phase separation (NIPS) methods. Hydrophilically-modified PVDF membranes were successfully prepared by blending in hydrophilic polymer polyvinyl alcohol (PVA) at 140 °C. A series of PVDF/PVA blend membranes was prepared at different total polymer concentrations and blend ratios. The morphological analysis via SEM indicated that the formation mechanism of these hydrophilically-modified membranes was a combined NIPS and TIPS process. As the total polymer concentration increased, the tensile strength of the membranes increased; meanwhile, the membrane pore size, porosity and water flux decreased. With the PVDF/PVA blend ratio increased from 10:0 to 8:2, the membrane pore size and water flux increased. The dynamic water contact angle of these membranes showed that the hydrophilic properties of PVDF/PVA blend membranes were prominently improved. The higher hydrophilicity of the membranes resulted in reduced membrane resistance and, hence, higher permeability. The total resistance Rt of the modified PVDF membranes decreased significantly as the hydrophilicity increased. The irreversible fouling related to pore blocking and adsorption fouling onto the membrane surface was minimal, indicating good antifouling properties. PMID:27869711

Highly Concentrated Nebular Noble Gases in Porous Nanocarbon Separates from the Saratov (L4) Meteorite

NASA Astrophysics Data System (ADS)

Amari, Sachiko; Matsuda, Jun-ichi; Stroud, Rhonda M.; Chisholm, Matthew F.

2013-11-01

The majority of heavy noble gases (Ar, Kr, and Xe) in primitive meteorites are stored in a poorly understood phase called Q. Although Q is thought to be carbonaceous, the full identity of the phase has remained elusive for almost four decades. In order to better characterize phase Q and, in turn, the early solar nebula, we separated carbon-rich fractions from the Saratov (L4) meteorite. We chose this meteorite because Q is most resistant in thermal alteration among carbonaceous noble gas carriers in meteorites and we hoped that, in this highly metamorphosed meteorite, Q would be present but not diamond: these two phases are very difficult to separate from each other. One of the fractions, AJ, has the highest 132Xe concentration of 2.1 × 10-6 cm3 STP g-1, exceeding any Q-rich fractions that have yet been analyzed. Transmission electron microscopy studies of the fraction AJ and a less Q-rich fraction AI indicate that they both are primarily porous carbon that consists of domains with short-range graphene orders, with variable packing in three dimensions, but no long-range graphitic order. The relative abundance of Xe and C atoms (6:109) in the separates indicates that individual noble gas atoms are associated with only a minor component of the porous carbon, possibly one or more specific arrangements of the nanoparticulate graphene.

Preparation and Characterization of Hydrophilically Modified PVDF Membranes by a Novel Nonsolvent Thermally Induced Phase Separation Method.

PubMed

Hu, Ningen; Xiao, Tonghu; Cai, Xinhai; Ding, Lining; Fu, Yuhua; Yang, Xing

2016-11-18

In this study, a nonsolvent thermally-induced phase separation (NTIPS) method was first proposed to fabricate hydrophilically-modified poly(vinylidene fluoride) (PVDF) membranes to overcome the drawbacks of conventional thermally-induced phase separation (TIPS) and nonsolvent-induced phase separation (NIPS) methods. Hydrophilically-modified PVDF membranes were successfully prepared by blending in hydrophilic polymer polyvinyl alcohol (PVA) at 140 °C. A series of PVDF/PVA blend membranes was prepared at different total polymer concentrations and blend ratios. The morphological analysis via SEM indicated that the formation mechanism of these hydrophilically-modified membranes was a combined NIPS and TIPS process. As the total polymer concentration increased, the tensile strength of the membranes increased; meanwhile, the membrane pore size, porosity and water flux decreased. With the PVDF/PVA blend ratio increased from 10:0 to 8:2, the membrane pore size and water flux increased. The dynamic water contact angle of these membranes showed that the hydrophilic properties of PVDF/PVA blend membranes were prominently improved. The higher hydrophilicity of the membranes resulted in reduced membrane resistance and, hence, higher permeability. The total resistance R t of the modified PVDF membranes decreased significantly as the hydrophilicity increased. The irreversible fouling related to pore blocking and adsorption fouling onto the membrane surface was minimal, indicating good antifouling properties.

Real-Time Atmospheric Phase Fluctuation Correction Using a Phased Array of Widely Separated Antennas: X-Band Results and Ka-Band Progress

NASA Astrophysics Data System (ADS)

Geldzahler, B.; Birr, R.; Brown, R.; Grant, K.; Hoblitzell, R.; Miller, M.; Woods, G.; Argueta, A.; Ciminera, M.; Cornish, T.; D'Addario, L.; Davarian, F.; Kocz, J.; Lee, D.; Morabito, D.; Tsao, P.; Jakeman-Flores, H.; Ott, M.; Soloff, J.; Denn, G.; Church, K.; Deffenbaugh, P.

2016-09-01

NASA is pursuing a demonstration of coherent uplink arraying at 7.145-7.190 GHz (X-band) and 30-31 GHz (Kaband) using three 12m diameter COTS antennas separated by 60m at the Kennedy Space Center in Florida. In addition, we have used up to three 34m antennas separated by 250m at the Goldstone Deep Space Communication Complex in California at X-band 7.1 GHz incorporating real-time correction for tropospheric phase fluctuations. Such a demonstration can enable NASA to design and establish a high power, high resolution, 24/7 availability radar system for (a) tracking and characterizing observations of Near Earth Objects (NEOs), (b) tracking, characterizing and determining the statistics of small-scale (≤10cm) orbital debris, (c) incorporating the capability into its space communication and navigation tracking stations for emergency spacecraft commanding in the Ka band era which NASA is entering, and (d) fielding capabilities of interest to other US government agencies. We present herein the results of our phased array uplink combining at near 7.17 and 8.3 GHz using widely separated antennas demonstrations at both locales, the results of a study to upgrade from a communication to a radar system, and our vision for going forward in implementing a high performance, low lifecycle cost multi-element radar array.

Micelle-induced depletion interaction and resultant structure in charged colloidal nanoparticle system

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

Ray, D.; Aswal, V. K., E-mail: vkaswal@barc.gov.in; Kohlbrecher, J.

2015-04-28

The evolution of the interaction and the resultant structure in the mixed system of anionic silica nanoparticles (Ludox LS30) and non-ionic surfactant decaethylene glycol monododecylether (C12E10), undergoing phase separation, have been studied using small-angle neutron scattering and dynamic light scattering. The measurements have been carried out for a fixed concentration of nanoparticle (1 wt. %) with varying concentration of surfactant (0 to 1 wt. %), in the absence and presence of an electrolyte. It is found that the micelles of non-ionic surfactant adsorb on the nanoparticle in the absence of electrolyte (form stable system), whereas these micelles become non-adsorbing in the presence of electrolytemore » (show phase separation). The phase separation arises because of C12E10 micelles, causing depletion interaction between nanoparticles and leading to their aggregation. The interaction is modeled by double Yukawa potential accounting for attractive depletion as well as repulsive electrostatic forces. Both the interactions (attraction and repulsion) are found to be of long-range. The nanoparticle aggregation (phase separation) is governed by the increase in the magnitude and the range of the depletion attraction with the increase in the surfactant concentration. The nanoparticle aggregates formed are quite large in size (order of micron) and are characterized by the surface fractal having simple cubic packing of nanoparticles within the aggregates.« less

Scaling behavior of nonisothermal phase separation.

PubMed

Rüllmann, Max; Alig, Ingo

2004-04-22

The phase separation process in a critical mixture of polydimethylsiloxane and polyethylmethylsiloxane (PDMS/PEMS, a system with an upper critical solution temperature) was investigated by time-resolved light scattering during continuous quenches from the one-phase into the two-phase region. Continuous quenches were realized by cooling ramps with different cooling rates kappa. Phase separation kinetics is studied by means of the temporal evolution of the scattering vector qm and the intensity Im at the scattering peak. The curves qm(t) for different cooling rates can be shifted onto a single mastercurve. The curves Im(t) show similar behavior. As shift factors, a characteristic length Lc and a characteristic time tc are introduced. Both characteristic quantities depend on the cooling rate through power laws: Lc approximately kappa(-delta) and tc approximately kappa(-rho). Scaling behavior in isothermal critical demixing is well known. There the temporal evolutions of qm and Im for different quench depths DeltaT can be scaled with the correlation length xi and the interdiffusion coefficient D, both depending on DeltaT through critical power laws. We show in this paper that the cooling rate scaling in nonisothermal demixing is a consequence of the quench depth scaling in the isothermal case. The exponents delta and rho are related to the critical exponents nu and nu* of xi and D, respectively. The structure growth during nonisothermal demixing can be described with a semiempirical model based on the hydrodynamic coarsening mechanism well known in the isothermal case. In very late stages of nonisothermal phase separation a secondary scattering maximum appears. This is due to secondary demixing. We explain the onset of secondary demixing by a competition between interdiffusion and coarsening. (c) 2004 American Institute of Physics