Process for recovering chaotropic anions from an aqueous solution also containing other ions

DOEpatents

Rogers, Robin; Horwitz, E. Philip; Bond, Andrew H.

1999-01-01

A solid/liquid process for the separation and recovery of chaotropic anions from an aqueous solution is disclosed. The solid support comprises separation particles having surface-bonded poly(ethylene glycol) groups, whereas the aqueous solution from which the chaotropic anions are separated contains a poly(ethylene glycol) liquid/liquid biphase-forming amount of a dissolved salt (lyotrope). A solid/liquid phase admixture of separation particles containing bound chaotropic anions in such an aqueous solution is also contemplated, as is a chromatography apparatus containing that solid/liquid phase admixture.

Process for recovering chaotropic anions from an aqueous solution also containing other ions

DOEpatents

Rogers, R.; Horwitz, E.P.; Bond, A.H.

1999-03-30

A solid/liquid process for the separation and recovery of chaotropic anions from an aqueous solution is disclosed. The solid support comprises separation particles having surface-bonded poly(ethylene glycol) groups, whereas the aqueous solution from which the chaotropic anions are separated contains a poly(ethylene glycol) liquid/liquid biphase-forming amount of a dissolved salt (lyotrope). A solid/liquid phase admixture of separation particles containing bound chaotropic anions in such an aqueous solution is also contemplated, as is a chromatography apparatus containing that solid/liquid phase admixture. 19 figs.

Tube Radial Distribution Flow Separation in a Microchannel Using an Ionic Liquid Aqueous Two-Phase System Based on Phase Separation Multi-Phase Flow.

PubMed

Nagatani, Kosuke; Shihata, Yoshinori; Matsushita, Takahiro; Tsukagoshi, Kazuhiko

2016-01-01

Ionic liquid aqueous two-phase systems were delivered into a capillary tube to achieve tube radial distribution flow (TRDF) or annular flow in a microspace. The phase diagram, viscosity of the phases, and TRDF image of the 1-butyl-3-methylimidazolium chloride and NaOH system were examined. The TRDF was formed with inner ionic liquid-rich and outer ionic liquid-poor phases in the capillary tube. The phase configuration was explained using the viscous dissipation principle. We also examined the distribution of rhodamine B in a three-branched microchannel on a microchip with ionic liquid aqueous two-phase systems for the first time.

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.

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.

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.

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.

Crystallization process

DOEpatents

Adler, Robert J.; Brown, William R.; Auyang, Lun; Liu, Yin-Chang; Cook, W. Jeffrey

1986-01-01

An improved crystallization process is disclosed for separating a crystallizable material and an excluded material which is at least partially excluded from the solid phase of the crystallizable material obtained upon freezing a liquid phase of the materials. The solid phase is more dense than the liquid phase, and it is separated therefrom by relative movement with the formation of a packed bed of solid phase. The packed bed is continuously formed adjacent its lower end and passed from the liquid phase into a countercurrent flow of backwash liquid. The packed bed extends through the level of the backwash liquid to provide a drained bed of solid phase adjacent its upper end which is melted by a condensing vapor.

Purification of flavonoids from licorice using an off-line preparative two-dimensional normal-phase liquid chromatography/reversed-phase liquid chromatography method.

PubMed

Fan, Yunpeng; Fu, Yanhui; Fu, Qing; Cai, Jianfeng; Xin, Huaxia; Dai, Mei; Jin, Yu

2016-07-01

An orthogonal (71.9%) off-line preparative two-dimensional normal-phase liquid chromatography/reversed-phase liquid chromatography method coupled with effective sample pretreatment was developed for separation and purification of flavonoids from licorice. Most of the nonflavonoids were firstly removed using a self-made Click TE-Cys (60 μm) solid-phase extraction. In the first dimension, an industrial grade preparative chromatography was employed to purify the crude flavonoids. Click TE-Cys (10 μm) was selected as the stationary phase that provided an excellent separation with high reproducibility. Ethyl acetate/ethanol was selected as the mobile phase owing to their excellent solubility for flavonoids. Flavonoids co-eluted in the first dimension were selected for further purification using reversed-phase liquid chromatography. Multiple compounds could be isolated from one normal-phase fraction and some compounds with bad resolution in one-dimensional liquid chromatography could be prepared in this two-dimensional system owing to the orthogonal separation. Moreover, this two-dimensional liquid chromatography method was beneficial for the preparation of relatively trace flavonoid compounds, which were enriched in the first dimension and further purified in the second dimension. Totally, 24 flavonoid compounds with high purity were obtained. The results demonstrated that the off-line two-dimensional liquid chromatography method was effective for the preparative separation and purification of flavonoids from licorice. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Pharmaceutical Perspective on Opalescence and Liquid-Liquid Phase Separation in Protein Solutions.

PubMed

Raut, Ashlesha S; Kalonia, Devendra S

2016-05-02

Opalescence in protein solutions reduces aesthetic appeal of a formulation and can be an indicator of the presence of aggregates or precursor to phase separation in solution signifying reduced product stability. Liquid-liquid phase separation of a protein solution into a protein-rich and a protein-poor phase has been well-documented for globular proteins and recently observed for monoclonal antibody solutions, resulting in physical instability of the formulation. The present review discusses opalescence and liquid-liquid phase separation (LLPS) for therapeutic protein formulations. A brief discussion on theoretical concepts based on thermodynamics, kinetics, and light scattering is presented. This review also discusses theoretical concepts behind intense light scattering in the vicinity of the critical point termed as "critical opalescence". Both opalescence and LLPS are affected by the formulation factors including pH, ionic strength, protein concentration, temperature, and excipients. Literature reports for the effect of these formulation factors on attractive protein-protein interactions in solution as assessed by the second virial coefficient (B2) and the cloud-point temperature (Tcloud) measurements are also presented. The review also highlights pharmaceutical implications of LLPS in protein solutions.

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).

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. .

Analysis of effluent after anaerobic digestion of liquid phase separated from liquidized garbage.

PubMed

Inoue, Seiichi; Tsukahara, Kenichiro; Sawayama, Shigeki

2002-01-01

The organic compositions of the liquid phase separated from liquidized garbage as the influent and its effluent after anaerobic digestion at an overloading rate were analyzed. A large amount of organic acids was found in the effluent. The accumulation of organic acids suggests that the rate of methanogenesis is lower than that of acidogenesis.

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.

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.

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.

Measurement of dielectric constant of organic solvents by indigenously developed dielectric probe

NASA Astrophysics Data System (ADS)

Keshari, Ajay Kumar; Rao, J. Prabhakar; Rao, C. V. S. Brahmmananda; Ramakrishnan, R.; Ramanarayanan, R. R.

2018-04-01

The extraction, separation and purification of actinides (uranium and plutonium) from various matrices are an important step in nuclear fuel cycle. One of the separation process adopted in an industrial scale is the liquid-liquid extraction or solvent extraction. Liquid-liquid extraction uses a specific ligand/extractant in conjunction with suitable diluent. Solvent extraction or liquid-liquid extraction, involves the partitioning of the solute between two immiscible phases. In most cases, one of the phases is aqueous, and the other one is an organic solvent. The solvent used in solvent extraction should be selective for the metal of interest, it should have optimum distribution ratio, and the loaded metal from the organic phase should be easily stripped under suitable experimental conditions. Some of the important physical properties which are important for the solvent are density, viscosity, phase separation time, interfacial surface tension and the polarity of the extractant.

Thermoset molecular composites

DOEpatents

Benicewicz, Brian C.; Douglas, Elliot P.; Hjelm, Jr., Rex P.

1996-01-01

A polymeric composition including a liquid crystalline polymer and a thermosettable liquid crystalline monomer matrix, said polymeric composition characterized by a phase separation on the scale of less than about 500 Angstroms and a polymeric composition including a liquid crystalline polymer and a liquid crystalline thermoset matrix, said polymeric composition characterized by a phase separation on the scale of less than about 500 Angstroms are disclosed.

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.

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.

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.

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.

The effect of liquid-liquid phase separation of glass on the properties and crystallization behavior

NASA Technical Reports Server (NTRS)

Li, J. Z.

1985-01-01

A theoretical discussion is given of the phase separation mechanism of amorphous materials. This includes nucleus growth, spinoidal decomposition, and nuclei agglomeration and coarsening. Various types of glass are analyzed.

Process for recovering pertechnetate ions from an aqueous solution also containing other ions

DOEpatents

Rogers, Robin; Horwitz, E. Philip; Bond, Andrew H.

1997-01-01

A solid/liquid process for the separation and recovery of TcO.sub.4.sup.-1 ions from an aqueous solution is disclosed. The solid support comprises separation particles having surface-bonded poly(ethylene glycol) groups; whereas the aqueous solution from which the TcO.sub.4.sup.-1 ions are separated contains a poly(ethylene glycol) liquid/liquid biphase-forming amount of a dissolved salt. A solid/liquid phase admixture of separation particles containing bound TcO.sub.4.sup.-1 ions in such an aqueous solution that is free from MoO.sub.4.sup.-2 ions is also contemplated, as is a chromatography apparatus containing that solid/liquid phase admixture.

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.

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.

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.

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.

Separation Of Liquid And Gas In Zero Gravity

NASA Technical Reports Server (NTRS)

Howard, Frank S.; Fraser, Wilson S.

1991-01-01

Pair of reports describe scheme for separating liquid from gas so liquid could be pumped. Designed to operate in absence of gravitation. Jet of liquid, gas, or liquid/gas mixture fed circumferentially into cylindrical tank filled with liquid/gas mixture. Jet starts liquid swirling. Swirling motion centrifugally separates liquid from gas. Liquid then pumped from tank at point approximately diametrically opposite point of injection of jet. Vortex phase separator replaces such devices as bladders and screens. Requires no components inside tank. Pumps for gas and liquid outside tank and easily accessible for maintenance and repairs.

Process for separating and recovering an anionic dye from an aqueous solution

DOEpatents

Rogers, Robin; Horwitz, E. Philip; Bond, Andrew H.

1998-01-01

A solid/liquid phase process for the separation and recovery of an anionic dye from an aqueous solution is disclosed. The solid phase comprises separation particles having surface-bonded poly(ethylene glycol) groups, whereas the aqueous solution from which the anionic dye molecules are separated contains a poly(ethylene glycol) liquid/liquid biphase-forming amount of a dissolved lyotropic salt. After contact between the aqueous solution and separation particles, the anionic dye is bound to the particles. The bound anionic dye molecules are freed from the separation particles by contacting the anionic dye-bound particles with an aqueous solution that does not contain a poly(ethylene glycol) liquid/liquid biphase-forming amount of a dissolved lyotropic salt to form an aqueous anionic dye solution whose anionic dye concentration is preferably higher than that of the initial dye-containing solution.

Centrifugal pyrocontactor

DOEpatents

Chow, Lorac S.; Leonard, Ralph A.

1993-01-01

A method for mixing and separating immiscible liquid salts and liquid metals in a centrifugal contractor. The method includes introducing the liquids into an annular mixing zone and intensely mixing the liquids using vertical vanes attached to a rotor cooperating with vertical baffles, a horizontal baffle, and bottom vanes attached to the contactor housing. The liquids enter the contactor in the range of 700-800 degrees Celsius. The liquids are separated in the rotor into a dense phase and a light phase which are discharged from the contactor.

Centrifugal pyrocontactor

DOEpatents

Chow, L.S.; Leonard, R.A.

1993-10-19

A method is described for mixing and separating immiscible liquid salts and liquid metals in a centrifugal contractor. The method includes introducing the liquids into an annular mixing zone and intensely mixing the liquids using vertical vanes attached to a rotor cooperating with vertical baffles, a horizontal baffle, and bottom vanes attached to the contactor housing. The liquids enter the contactor in the range of 700-800 degrees Celsius. The liquids are separated in the rotor into a dense phase and a light phase which are discharged from the contactor. 6 figures.

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.

Computation of liquid-liquid equilibria and phase stabilities: implications for RH-dependent gas/particle partitioning of organic-inorganic aerosols

NASA Astrophysics Data System (ADS)

Zuend, A.; Marcolli, C.; Peter, T.; Seinfeld, J. H.

2010-05-01

Semivolatile organic and inorganic aerosol species partition between the gas and aerosol particle phases to maintain thermodynamic equilibrium. Liquid-liquid phase separation into an organic-rich and an aqueous electrolyte phase can occur in the aerosol as a result of the salting-out effect. Such liquid-liquid equilibria (LLE) affect the gas/particle partitioning of the different semivolatile compounds and might significantly alter both particle mass and composition as compared to a one-phase particle. We present a new liquid-liquid equilibrium and gas/particle partitioning model, using as a basis the group-contribution model AIOMFAC (Zuend et al., 2008). This model allows the reliable computation of the liquid-liquid coexistence curve (binodal), corresponding tie-lines, the limit of stability/metastability (spinodal), and further thermodynamic properties of the phase diagram. Calculations for ternary and multicomponent alcohol/polyol-water-salt mixtures suggest that LLE are a prevalent feature of organic-inorganic aerosol systems. A six-component polyol-water-ammonium sulphate system is used to simulate effects of relative humidity (RH) and the presence of liquid-liquid phase separation on the gas/particle partitioning. RH, salt concentration, and hydrophilicity (water-solubility) are identified as key features in defining the region of a miscibility gap and govern the extent to which compound partitioning is affected by changes in RH. The model predicts that liquid-liquid phase separation can lead to either an increase or decrease in total particulate mass, depending on the overall composition of a system and the particle water content, which is related to the hydrophilicity of the different organic and inorganic compounds. Neglecting non-ideality and liquid-liquid phase separations by assuming an ideal mixture leads to an overestimation of the total particulate mass by up to 30% for the composition and RH range considered in the six-component system simulation. For simplified partitioning parametrizations, we suggest a modified definition of the effective saturation concentration, C*j, by including water and other inorganics in the absorbing phase. Such a C*j definition reduces the RH-dependency of the gas/particle partitioning of semivolatile organics in organic-inorganic aerosols by an order of magnitude as compared to the currently accepted definition, which considers the organic species only.

Centrifugal contactor modified for end stage operation in a multistage system

DOEpatents

Jubin, Robert T.

1990-01-01

A cascade formed of a plurality of centrifugal contactors useful for countercurrent solvent extraction processes such as utilizable for the reprocessing of nuclear reactor fuels is modified to permit operation in the event one or both end stages of the cascade become inoperative. Weir assemblies are connected to each of the two end stages by suitable conduits for separating liquids discharged from an inoperative end stage based upon the weight of the liquid phases uses in the solvent extraction process. The weir assembly at one end stage is constructed to separate and discharge the heaviest liquid phase while the weir assembly at the other end stage is constructed to separate and discharge the lightest liquid phase. These weir assemblies function to keep the liquid discharge from an inoperative end stages on the same weight phase a would occur from an operating end stage.

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.

Protein separations using enhanced-fluidity liquid chromatography.

PubMed

Bennett, Raffeal; Olesik, Susan V

2017-11-10

Enhanced-fluidity liquid chromatography (EFLC) methods using methanol/H 2 O/CO 2 and hydrophilic interaction liquid chromatography (HILIC) were explored for the separation of proteins and peptides. EFLC is a separation mode that uses a mobile phase made of conventional solvents combined with liquid carbon dioxide (CO 2 ) in subcritical conditions. The addition of liquid CO 2 enhances diffusivity and decreases viscosity while maintaining mixture polarity, which typically results in reduced time of analysis. TFA additive and elevated temperature were leveraged as key factors in the separation of a 13-analyte intact protein mixture in under 5min. Under these conditions EFLC showed modest improvement in terms of peak asymmetry and analysis time over the competing ACN/H 2 O separation. Protein analytes detected by electrospray ionization - quadrupole time of flight, were shown to be unaffected by the addition of CO 2 in the mobile phase. Herein, the feasibility of separating hydrophilic proteins up to 80kDa (with transferrin) is demonstrated for CO 2 -containing mobile phases. Copyright © 2017 Elsevier B.V. All rights reserved.

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.

Cleaning and dewatering fine coal

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

Yoon, Roe-Hoan; Eraydin, Mert K.; Freeland, Chad

Fine coal is cleaned of its mineral matter impurities and dewatered by mixing the aqueous slurry containing both with a hydrophobic liquid, subjecting the mixture to a phase separation. The resulting hydrophobic liquid phase contains coal particles free of surface moisture and droplets of water stabilized by coal particles, while the aqueous phase contains the mineral matter. By separating the entrained water droplets from the coal particles mechanically, a clean coal product of substantially reduced mineral matter and moisture contents is obtained. The spent hydrophobic liquid is separated from the clean coal product and recycled. The process can also bemore » used to separate one type of hydrophilic particles from another by selectively hydrophobizing one.« less

Process for recovering pertechnetate ions from an aqueous solution also containing other ions

DOEpatents

Rogers, R.; Horwitz, E.P.; Bond, A.H.

1997-02-18

A solid/liquid process for the separation and recovery of TcO{sub 4}{sup {minus}1} ions from an aqueous solution is disclosed. The solid support comprises separation particles having surface-bonded poly(ethylene glycol) groups; whereas the aqueous solution from which the TcO{sub 4}{sup {minus}1} ions are separated contains a poly(ethylene glycol) liquid/liquid biphase-forming amount of a dissolved salt. A solid/liquid phase admixture of separation particles containing bound TcO{sub 4}{sup {minus}1} ions in such an aqueous solution that is free from MoO{sub 4}{sup {minus}2} ions is also contemplated, as is a chromatography apparatus containing that solid/liquid phase admixture. 15 figs.

Process for separating and recovering an anionic dye from an aqueous solution

DOEpatents

Rogers, R.; Horwitz, E.P.; Bond, A.H.

1998-01-13

A solid/liquid phase process for the separation and recovery of an anionic dye from an aqueous solution is disclosed. The solid phase comprises separation particles having surface-bonded poly(ethylene glycol) groups, whereas the aqueous solution from which the anionic dye molecules are separated contains a poly(ethylene glycol) liquid/liquid biphase-forming amount of a dissolved lyotropic salt. After contact between the aqueous solution and separation particles, the anionic dye is bound to the particles. The bound anionic dye molecules are freed from the separation particles by contacting the anionic dye-bound particles with an aqueous solution that does not contain a poly(ethylene glycol) liquid/liquid biphase-forming amount of a dissolved lyotropic salt to form an aqueous anionic dye solution whose anionic dye concentration is preferably higher than that of the initial dye-containing solution. 7 figs.

Liquid-liquid separation in solutions of normal and sickle cell hemoglobin

NASA Astrophysics Data System (ADS)

Galkin, Oleg; Chen, Kai; Nagel, Ronald L.; Elison Hirsch, Rhoda; Vekilov, Peter G.

2002-06-01

We show that in solutions of human hemoglobin (Hb)oxy- and deoxy-Hb A or Sof near-physiological pH, ionic strength, and Hb concentration, liquid-liquid phase separation occurs reversibly and reproducibly at temperatures between 35 and 40°C. In solutions of deoxy-HbS, we demonstrate that the dense liquid droplets facilitate the nucleation of HbS polymers, whose formation is the primary pathogenic event for sickle cell anemia. In view of recent results that shifts of the liquid-liquid separation phase boundary can be achieved by nontoxic additives at molar concentrations up to 30 times lower than the protein concentrations, these findings open new avenues for the inhibition of the HbS polymerization.

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.

Computation of liquid-liquid equilibria and phase stabilities: implications for RH-dependent gas/particle partitioning of organic-inorganic aerosols

NASA Astrophysics Data System (ADS)

Zuend, A.; Marcolli, C.; Peter, T.; Seinfeld, J. H.

2010-08-01

Semivolatile organic and inorganic aerosol species partition between the gas and aerosol particle phases to maintain thermodynamic equilibrium. Liquid-liquid phase separation into an organic-rich and an aqueous electrolyte phase can occur in the aerosol as a result of the salting-out effect. Such liquid-liquid equilibria (LLE) affect the gas/particle partitioning of the different semivolatile compounds and might significantly alter both particle mass and composition as compared to a one-phase particle. We present a new liquid-liquid equilibrium and gas/particle partitioning model, using as a basis the group-contribution model AIOMFAC (Zuend et al., 2008). This model allows the reliable computation of the liquid-liquid coexistence curve (binodal), corresponding tie-lines, the limit of stability/metastability (spinodal), and further thermodynamic properties of multicomponent systems. Calculations for ternary and multicomponent alcohol/polyol-water-salt mixtures suggest that LLE are a prevalent feature of organic-inorganic aerosol systems. A six-component polyol-water-ammonium sulphate system is used to simulate effects of relative humidity (RH) and the presence of liquid-liquid phase separation on the gas/particle partitioning. RH, salt concentration, and hydrophilicity (water-solubility) are identified as key features in defining the region of a miscibility gap and govern the extent to which compound partitioning is affected by changes in RH. The model predicts that liquid-liquid phase separation can lead to either an increase or decrease in total particulate mass, depending on the overall composition of a system and the particle water content, which is related to the hydrophilicity of the different organic and inorganic compounds. Neglecting non-ideality and liquid-liquid phase separations by assuming an ideal mixture leads to an overestimation of the total particulate mass by up to 30% for the composition and RH range considered in the six-component system simulation. For simplified partitioning parametrizations, we suggest a modified definition of the effective saturation concentration, Cj*, by including water and other inorganics in the absorbing phase. Such a Cj* definition reduces the RH-dependency of the gas/particle partitioning of semivolatile organics in organic-inorganic aerosols by an order of magnitude as compared to the currently accepted definition, which considers the organic species only.

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.

Low gravity phase separator

NASA Technical Reports Server (NTRS)

Smoot, G. F.; Pope, W. L.; Smith, L. (Inventor)

1977-01-01

An apparatus is described for phase separating a gas-liquid mixture as might exist in a subcritical cryogenic helium vessel for cooling a superconducting magnet at low gravity such as in planetary orbit, permitting conservation of the liquid and extended service life of the superconducting magnet.

HIGH PERFORMANCE LIQUID CHROMATOGRAPHIC SEPARATION OF THE ENANTIOMERS OF ORGANOPHOSPHORUS PESTICIDES ON POLYSACCHARIDE CHIRAL STATIONARY PHASES

EPA Science Inventory

High-performance liquid chromatographic separation of the individual enantiomers of 12 organophosphorus pesticides (OPs) was obtained on polysaccharide enantioselective HPLC columns using alkane-alcohol mobile phase. The OP pesticides were crotoxyphos, dialifor, fonofos, fenamiph...

Superfluid helium 2 liquid-vapor phase separation: Technology assessment

NASA Technical Reports Server (NTRS)

Lee, J. M.

1984-01-01

A literature survey of helium 2 liquid vapor phase separation is presented. Currently, two types of He 2 phase separators are being investigated: porous, sintered metal plugs and the active phase separator. The permeability K(P) shows consistency in porous plug geometric characterization. Both the heat and mass fluxes increase with K(P). Downstream pressure regulation to adjust for varying heat loads and both temperatures is possible. For large dynamic heat loads, the active phase separator shows a maximum heat rejection rate of up to 2 W and bath temperature stability of 0.1 mK. Porous plug phase separation performance should be investigated for application to SIRTF and, in particular, that plugs of from 10 to the minus ninth square centimeters to 10 to the minus eighth square centimeters in conjunction with downstream pressure regulation be studied.

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.

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

Exploring Liquid Sequential Injection Chromatography to Teach Fundamentals of Separation Methods: A Very Fast Analytical Chemistry Experiment

ERIC Educational Resources Information Center

Penteado, Jose C.; Masini, Jorge Cesar

2011-01-01

Influence of the solvent strength determined by the addition of a mobile-phase organic modifier and pH on chromatographic separation of sorbic acid and vanillin has been investigated by the relatively new technique, liquid sequential injection chromatography (SIC). This technique uses reversed-phase monolithic stationary phase to execute fast…

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.

LIGHT NONAQUEOUS PHASE LIQUIDS

EPA Science Inventory

Nonaqueous phase liquids (NAPLS) are hydrocarbons that exist as a separate, immiscible phase when in contact with water and/or air. ifferences in the physical and chemical properties of water and NAPL result in the formation of a physical interface between the liquids which preve...

Organization out of disorder: liquid-liquid phase separation in plants.

PubMed

Cuevas-Velazquez, Cesar L; Dinneny, José R

2018-05-30

Membraneless compartments are formed from the dynamic physical association of proteins and RNAs through liquid-liquid phase separation, and have recently emerged as an exciting new mechanism to explain the dynamic organization of biochemical processes in the cell. In this review, we provide an overview of the current knowledge of the process of phase separation in plants and other eukaryotes. We discuss specific examples of liquid-like membraneless compartments found in green plants, their composition, and the intriguing prevalence of proteins with intrinsically disordered domains. Finally, we speculate on the function of disordered proteins in regulating the formation of membraneless compartments and how their conformational flexibility may be important for molecular memory and for sensing perturbations in the physicochemical environment of the cell, particularly important processes in sessile organisms. Copyright © 2018 The Authors. Published by Elsevier Ltd.. All rights reserved.

Gas chromatography on wall-coated open-tubular columns with ionic liquid stationary phases.

PubMed

Poole, Colin F; Lenca, Nicole

2014-08-29

Ionic liquids have moved from novel to practical stationary phases for gas chromatography with an increasing portfolio of applications. Ionic liquids complement conventional stationary phases because of a combination of thermophysical and solvation properties that only exist for ionic solvents. Their high thermal stability and low vapor pressure makes them suitable as polar stationary phases for separations requiring high temperatures. Ionic liquids are good solvents and can be used to expand the chemical space for separations. They are the only stationary phases with significant hydrogen-bond acidity in common use; they extend the hydrogen-bond basicity of conventional stationary phases; they are as dipolar/polarizable as the most polar conventional stationary phases; and some ionic liquids are significantly less cohesive than conventional polar stationary phases. Problems in column coating techniques and related low column performance, column activity, and stationary phase reactivity require further exploration as the reasons for these features are poorly understood at present. Copyright © 2014 Elsevier B.V. All rights reserved.

SEPARATION AND QUANTITATION OF NITROBENZENES AND THEIR REDUCTION PRODUCTS NITROANILINES AND PHENYLENEDIAMINES BY REVERSED=PHASE HIGH-PERFORMANCE LIQUID CHROMATOGRAPHY

EPA Science Inventory

A reversed-phase high-performance liquid chromatographic method for the separation and quantitation of a mixture consisting of nitrobenzene, dinitrobenzene isomers, 1,3,5-trinitrobenzene and their reduction products: aniline, nitroanilines and phenylenediamines has been developed...

Chembio extraction on a chip by nanoliter droplet ejection.

PubMed

Yu, Hongyu; Kwon, Jae Wan; Kim, Eun Sok

2005-03-01

This paper describes a novel liquid separation technique for chembio extraction by an ultrasonic nanoliter-liquid-droplet ejector built on a PZT sheet. This technique extracts material from an aqueous two-phase system (ATPS) in a precise amount through digital control of the number of nanoliter droplets, without any mixing between the two liquids in the ATPS. The ultrasonic droplet ejector uses an acoustic streaming effect produced by an acoustic beam focused on the liquid surface, and ejects liquid droplets only from the liquid surface without disturbing most of the liquid below the surface. This unique characteristic of the focused acoustic beam is perfect (1) for separating a top-layer liquid (from the bulk of liquid) that contains particles of interest or (2) for recovering a top-layer liquid that has different phase from a bottom-layer liquid. Three kinds of liquid extraction are demonstrated with the ultrasonic droplet ejector: (1) 16 microl of top layer in Dextran-polyethylene glycol-water ATPS (aqueous two-phase system) is recovered within 20 s; (2) micron sized particles that float on water surface are ejected out with water droplets; and (3) oil layer on top of water is separated out.

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.

Normal Gravity Testing of a Microchannel Phase Separator for In Situ Resource Utilization

NASA Technical Reports Server (NTRS)

TeGrotenhuis, Ward E.; Stenkamp, Victoria S.; McQuillen, John (Technical Monitor)

2001-01-01

A microchannel separator, with 2.7 millimeters as the smallest dimension, was tested, and a pore throat structure captured and removed liquid from a gas-liquid stream. The microchannel device was tested over a of gas and liquid flow rates ranging from 0.0005 up to 0. 14 volume fraction of liquid. Four liquids were tested with air. The biggest factor affecting the throughput is the capacity of liquid flow through the pore throat, which is dictated by permeability, liquid viscosity, flow area, pore throat thickness, and pressure difference across the pore throat. Typically, complete separation of gas and liquid fractions was lost when the liquid flow rate reached about 40 to 60% of the pore throat capacity. However, this could occur over a range of 10 to 90% utilization of pore throat capacity. Breakthrough occurs in the microchannel phase separator at conditions similar to the annular to plug flow transition of two-phase microgravity pipe flow implying that operating in the proper flow regime is crucial. Analysis indicates that the Bond number did not affect performance, supporting the premise that hydrodynamic, interfacial, and capillary forces are more important than gravity. However, the relative importance of gravity is better discerned through testing under reduced gravity conditions.

On-line comprehensive two-dimensional normal-phase liquid chromatography×reversed-phase liquid chromatography for preparative isolation of toad venom.

PubMed

Li, Jia-Fu; Fang, Hua; Yan, Xia; Chang, Fang-Rong; Wu, Zhen; Wu, Yun-Long; Qiu, Ying-Kun

2016-07-22

An on-line comprehensive preparative two-dimensional normal-phase liquid chromatography×reversed-phase liquid chromatography (2D NPLC×RPLC) system was constructed with a newly developed vacuum evaporation assisted adsorption (VEAA) interface, allowing fast removal of NPLC solvent in the vacuum condition and successfully solving the solvent incompatibility problem between NPLC and RPLC. The system achieved on-line solvent exchange within the two dimensions and its performance was illustrated by gram-scale isolation of crude extract from the venom of Bufo bufo gargarizans. Within separation time of ∼20h, 19 compounds were obtained with high purity in a single run. With the VEAA interface, the 2D system exhibited apparent advantages in separation efficiency and automation compared with conventional methods, indicating its promising application in the routine separation process for complicated natural products. Copyright © 2016 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.

New porous monolithic membranes based on supported ionic liquid-like phases for oil/water separation and homogenous catalyst immobilisation.

PubMed

Porcar, Raúl; Nuevo, Daniel; García-Verdugo, Eduardo; Lozano, Pedro; Sanchez-Marcano, José; Burguete, M Isabel; Luis, Santiago V

2018-03-07

Porous monolithic advanced functional materials based on supported ionic liquid-like phase (SILLP) systems were used for the preparation of oleophilic and hydrophobic cylindrical membranes and successfully tested as eco-friendly and safe systems for oil/water separation and for the continuous integration of catalytic and separation processes in an aqueous-organic biphasic reaction system.

Dynamic evolution of liquid–liquid phase separation during continuous cooling

DOE PAGES

Imhoff, Seth D.; Gibbs, Paul J.; Katz, Martha R.; ...

2015-01-06

Solidification from a multiphase fluid involves many unknown quantities due to the difficulty of predicting the impact of fluid flow on chemical partitioning. Real-time x-ray radiography was used to observe liquid-liquid phase separation in Al 90In 10 prior to solidification. Quantitative image analysis was used to measure the motion and population characteristics of the dispersed indium-rich liquid phase during cooling. Here we determine that the droplet growth characteristics resemble well known steady-state coarsening laws with likely enhancement by concurrent growth due to supersaturation. Simplistic views of droplet motion are found to be insufficient until late in the reaction due tomore » a hydrodynamic instability caused by the large density difference between the dispersed and matrix liquid phases.« less

Phase separation kinetics in immiscible liquids

NASA Technical Reports Server (NTRS)

Ng, Lee H.; Sadoway, Donald R.

1987-01-01

The kinetics of phase separation in the succinonitrile-water system are being investigated. Experiments involve initial physical mixing of the two immiscible liquids at a temperature above the consolute, decreasing the temperature into the miscibility gap, followed by iamging of the resultant microstructure as it evolves with time. Refractive index differences allow documentation of the changing microstructures by noninvasive optical techniques without the need to quench the liquid structures for analysis.

Phase separation kinetics in immiscible liquids

NASA Technical Reports Server (NTRS)

Sadoway, D. R.

1986-01-01

The kinetics of phase separation in the succinonitrile-water system are being investigated. Experiments involve initial physical mixing of the two immiscible liquids at a temperature above the consolute, decreasing the temperature into the miscibility gap, followed by imaging of the resultant microstructure as it evolves with time. Refractive index differences allow documentation of the changing microstructures by noninvasive optical techniques without the need to quench the liquid structures for analysis.

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.

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.

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.

Fiber-based monolithic columns for liquid chromatography.

PubMed

Ladisch, Michael; Zhang, Leyu

2016-10-01

Fiber-based monoliths for use in liquid chromatographic separations are defined by columns packed with aligned fibers, woven matrices, or contiguous fiber structures capable of achieving rapid separations of proteins, macromolecules, and low molecular weight components. A common denominator and motivating driver for this approach, first initiated 25 years ago, was reducing the cost of bioseparations in a manner that also reduced residence time of retained components while achieving a high ratio of mass to momentum transfer. This type of medium, when packed into a liquid chromatography column, minimized the fraction of stagnant liquid and resulted in a constant plate height for non-adsorbing species. The uncoupling of dispersion from eluent flow rate enabled the surface chemistry of the stationary phase to be considered separately from fluid transport phenomena and pointed to new ways to apply chemistry for the engineering of rapid bioseparations. This paper addresses developments and current research on fiber-based monoliths and explains how the various forms of this type of chromatographic stationary phase have potential to provide new tools for analytical and preparative scale separations. The different stationary phases are discussed, and a model that captures the observed constant plate height as a function of mobile phase velocity is reviewed. Methods that enable hydrodynamically stable fiber columns to be packed and operated over a range of mobile phase flow rates, together with the development of new fiber chemistries, are shown to provide columns that extend the versatility of liquid chromatography using monoliths, particularly at the preparative scale. Graphical Abstract Schematic representation of a sample mixture being separated by a rolled-stationary phase column, resulting separated peaks shown in the chromatogram.

Mobile phase effects on the retention on polar columns with special attention to the dual hydrophilic interaction-reversed-phase liquid chromatography mechanism, a review.

PubMed

Jandera, Pavel; Hájek, Tomáš

2018-01-01

Hydrophilic interaction liquid chromatography on polar columns in aqueous-organic mobile phases has become increasingly popular for the separation of many biologically important compounds in chemical, environmental, food, toxicological, and other samples. In spite of many new applications appearing in literature, the retention mechanism is still controversial. This review addresses recent progress in understanding of the retention models in hydrophilic interaction liquid chromatography. The main attention is focused on the role of water, both adsorbed by the column and contained in the bulk mobile phase. Further, the theoretical retention models in the isocratic and gradient elution modes are discussed. The dual hydrophilic interaction liquid chromatography reversed-phase retention mechanism on polar columns is treated in detail, especially with respect to the practical use in one- and two-dimensional liquid chromatography separations. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

[Separation and purification of the components in Trachelospermum jasminoides by two dimensional hydrophilic interaction liquid chromatography- reversed-phase liquid chromatography].

PubMed

Jia, Youmei; Cai, Jianfeng; Xin, Huaxia; Feng, Jiatao; Fu, Yanhui; Fu, Qing; Jin, Yu

2017-06-08

A preparative two dimensional hydrophilic interaction liquid chromatography/reversed-phase liquid chromatography (Pre-2D-HILIC/RPLC) method was established to separate and purify the components in Trachelospermum jasminoides . The pigments and strongly polar components were removed from the crude extract after the active carbon decolorization and solid phase extraction processes. A Click XIon column (250 mm×20 mm, 10 μm) was selected as stationary phase and water-acetonitrile as mobile phases in the first dimensional HILIC. Finally, 15 fractions were collected under UV-triggered mode. In the second dimensional RPLC, a C18 column (250 mm×20 mm, 5 μm) was selected and water-acetonitrile was used as mobile phases. As a result, 14 compounds with high purity were obtained, which were further identified by mass spectrometry (MS) and nuclear magnetic resonance (NMR). Finally, 11 lignan compounds and three flavonoid compounds were obtained. The method has a good orthogonality, and can improve the resolution and the peak capacity. It is significant for the separation of complex components from Trachelospermum jasminoides .

Separation of Californium from other Actinides

DOEpatents

Mailen, J C; Ferris, L M

1973-09-25

A method is provided for separating californium from a fused fluoride composition containing californium and at least one element selected from the group consisting of plutonium, americium, curium, uranium, thorium, and protactinium which comprises contacting said fluoride composition with a liquid bismuth phase containing sufficient lithium or thorium to effect transfer of said actinides to the bismuth phase and then contacting the liquid bismuth phase with molten LiCl to effect selective transfer of californium to the chloride phase.

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).

Recovery of sugars from ionic liquid biomass liquor by solvent extraction

DOEpatents

Brennan, Timothy Charles R.; Holmes, Bradley M.; Simmons, Blake A.; Blanch, Harvey W.

2015-10-13

The present invention provides for a composition comprising a solution comprising (a) an ionic liquid (IL) or ionic liquid-aqueous (ILA) phase and (b) an organic phase, wherein the solution comprises a sugar and a boronic acid. The present invention also provides for a method of removing a sugar from a solution, comprising: (a) providing a solution comprising (i) an IL or ILA phase and (ii) an organic phase, wherein the solution comprises an IL, a sugar and a boronic acid; (b) contacting the sugar with the boronic acid to form a sugar-boronic acid complex, (c) separating the organic phase and the aqueous phase, wherein the organic phase contains the sugar-boronic acid complex, and optionally (d) separating the sugar from the organic phase.

On-line comprehensive two-dimensional normal-phase liquid chromatography × reversed-phase liquid chromatography for preparative isolation of Peucedanum praeruptorum.

PubMed

Wang, Xin-Yuan; Li, Jia-Fu; Jian, Ya-Mei; Wu, Zhen; Fang, Mei-Juan; Qiu, Ying-Kun

2015-03-27

A new on-line comprehensive preparative two-dimensional normal-phase liquid chromatography × reversed-phase liquid chromatography (2D NPLC × RPLC) system was developed for the separation of complicated natural products. It was based on the use of a silica gel packed medium-pressure column as the first dimension and an ODS preparative HPLC column as the second dimension. The two dimensions were connected with normal-phase (NP) and reversed-phase (RP) enrichment units, involving a newly developed airflow assisted adsorption (AAA) technique. The instrument operation and the performance of this NPLC × RPLC separation method were illustrated by gram-scale isolation of ethanol extract from the roots of Peucedanum praeruptorum. In total, 19 compounds with high purity were obtained via automated multi-step preparative separation in a short period of time using this system, and their structures were comprehensively characterized by ESI-MS, (1)H NMR, and (13)C NMR. Including two new compounds, five isomers in two groups with identical HPLC and TLC retention values were also obtained and identified by 1D NMR and 2D NMR. This is the first report of an NPLC × RPLC system successfully applied in an on-line preparative process. This system not only solved the interfacing problem of mobile-phase immiscibility caused by NP and RP separation, it also exhibited apparent advantages in separation efficiency and sample treatment capacity compared with conventional methods. Copyright © 2015 Elsevier B.V. All rights reserved.

Superamphiphobic Silicon-Nanowire-Embedded Microsystem and In-Contact Flow Performance of Gas and Liquid Streams.

PubMed

Ko, Dong-Hyeon; Ren, Wurong; Kim, Jin-Oh; Wang, Jun; Wang, Hao; Sharma, Siddharth; Faustini, Marco; Kim, Dong-Pyo

2016-01-26

Gas and liquid streams are invariably separated either by a solid wall or by a membrane for heat or mass transfer between the gas and liquid streams. Without the separating wall, the gas phase is present as bubbles in liquid or, in a microsystem, as gas plugs between slugs of liquid. Continuous and direct contact between the two moving streams of gas and liquid is quite an efficient way of achieving heat or mass transfer between the two phases. Here, we report a silicon nanowire built-in microsystem in which a liquid stream flows in contact with an underlying gas stream. The upper liquid stream does not penetrate into the lower gas stream due to the superamphiphobic nature of the silicon nanowires built into the bottom wall, thereby preserving the integrity of continuous gas and liquid streams, although they are flowing in contact. Due to the superamphiphobic nature of silicon nanowires, the microsystem provides the best possible interfacial mass transfer known to date between flowing gas and liquid phases, which can achieve excellent chemical performance in two-phase organic syntheses.

Separation of Poly(styrene-block-t-butyl methacrylate) Copolymers by Various Liquid Chromatography Techniques

PubMed Central

Šmigovec Ljubič, Tina; Pahovnik, David; Žigon, Majda; Žagar, Ema

2012-01-01

The separation of a mixture of three poly(styrene-block-t-butyl methacrylate) copolymers (PS-b-PtBMA), consisting of polystyrene (PS) blocks of similar length and t-butyl methacrylate (PtBMA) blocks of different lengths, was performed using various chromatographic techniques, that is, a gradient liquid chromatography on reversed-phase (C18 and C8) and normal-phase columns, a liquid chromatography under critical conditions for polystyrene as well as a fully automated two-dimensional liquid chromatography that separates block copolymers by chemical composition in the first dimension and by molar mass in the second dimension. The results show that a partial separation of the mixture of PS-b-PtBMA copolymers can be achieved only by gradient liquid chromatography on reversed-phase columns. The coelution of the two block copolymers is ascribed to a much shorter PtBMA block length, compared to the PS block, as well as a small difference in the length of the PtBMA block in two of these copolymers, which was confirmed by SEC-MALS and NMR spectroscopy. PMID:22489207

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.

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

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.

POLONIUM SEPARATION PROCESS

DOEpatents

Karraker, D.G.

1959-07-14

A liquid-liquid extraction process is presented for the recovery of polonium from lead and bismuth. According to the invention an acidic aqueous chloride phase containing the polonium, lead, and bismuth values is contacted with a tributyl phosphate ether phase. The polonium preferentially enters the organic phase which is then separated and washed with an aqueous hydrochloric solution to remove any lead or bismuth which may also have been extracted. The now highly purified polonium in the organic phase may be transferred to an aqueous solution by extraction with aqueous nitric acid.

Simplified thermodynamic functions for vapor-liquid phase separation and fountain effect pumps

NASA Technical Reports Server (NTRS)

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

1984-01-01

He-4 fluid handling devices near 2 K require novel components for non-Newtonian fluid transport in He II. Related sizing of devices has to be based on appropriate thermophysical property functions. The present paper presents simplified equilibrium state functions for porous media components which serve as vapor-liquid phase separators and fountain effect pumps.

Liquid Chromatography in 1982.

ERIC Educational Resources Information Center

Freeman, David H.

1982-01-01

Reviews trends in liquid chromatography including apparatus, factors affecting efficient separation of a mixture (peak sharpness and speed), simplified problem-solving, adsorption, bonded phase chromatography, ion selectivity, and size exclusion. The current trend is to control chemical selectivity by the liquid phase. (Author/JN)

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

For many years liquid scintillation cocktail (LSC) wastes have been generated and stored at Argonne National Laboratory (ANL). These wastes are stored in thousands of 10--20 m scintillation vials, many of which contain elements with Z > 88. Because storage space is limited, disposal of this waste is pressing. These wastes could be commercially incinerated if the radionuclides with Z>88 are reduced to sufficiently low levels. However, there is currently no deminimus level for these radionuclides, and separation techniques are still being tested. The University of Illinois is conducting experiments to separate radionuclides with Z > 88 from simulated LSCmore » wastes by using liquid-liquid extraction (LLX) and demulsification techniques. The actinide elements are removed from the LSC by extraction into an aqueous phase after the cocktail has been demulsified. The aqueous and organic phases are separated and the organic phase, now free from radionuclides with Z > 88, can be sent to a commercial incineration facility. The aqueous phase may be treated and disposed of using existing techniques. The LLX separation techniques used solutions of sodium oxalate, aluminum nitrate, and tetrasodium EDTA at varying concentrations. These extractants were mixed with the simulated waste in a 1:1 volume ratio. Using 1.0M Na{sub 4} EDTA salt solutions, decontamination ratios as high as 230 were achieved.« less

Development of an Efficient Meso- scale Multi-phase Flow Solver in Nuclear Applications

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

Lee, Taehun

2015-10-20

The proposed research aims at formulating a predictive high-order Lattice Boltzmann Equation for multi-phase flows relevant to nuclear energy related application - namely, saturated and sub-cooled boiling in reactors, and liquid- liquid mixing and extraction for fuel cycle separation. An efficient flow solver will be developed based on the Finite Element based Lattice Boltzmann Method (FE- LBM), accounting for phase-change heat transfer and capable of treating multiple phases over length scales from the submicron to the meter. A thermal LBM will be developed in order to handle adjustable Prandtl number, arbitrary specific heat ratio, a wide range of temperature variations,more » better numerical stability during liquid-vapor phase change, and full thermo-hydrodynamic consistency. Two-phase FE-LBM will be extended to liquid–liquid–gas multi-phase flows for application to high-fidelity simulations building up from the meso-scale up to the equipment sub-component scale. While several relevant applications exist, the initial applications for demonstration of the efficient methods to be developed as part of this project include numerical investigations of Critical Heat Flux (CHF) phenomena in nuclear reactor fuel bundles, and liquid-liquid mixing and interfacial area generation for liquid-liquid separations. In addition, targeted experiments will be conducted for validation of this advanced multi-phase model.« less

A green separation strategy for neodymium (III) from cobalt (II) and nickel (II) using an ionic liquid-based aqueous two-phase system.

PubMed

Chen, Yuehua; Wang, Huiyong; Pei, Yuanchao; Wang, Jianji

2018-05-15

It is significant to develop sustainable strategies for the selective separation of rare earth from transition metals from fundamental and practical viewpoint. In this work, an environmentally friendly solvent extraction approach has been developed to selectively separate neodymium (III) from cobalt (II) and nickel (II) by using an ionic liquid-based aqueous two phase system (IL-ATPS). For this purpose, a hydrophilic ionic liquid (IL) tetrabutylphosphonate nitrate ([P 4444 ][NO 3 ]) was prepared and used for the formation of an ATPS with NaNO 3 . Binodal curves of the ATPSs have been determined for the design of extraction process. The extraction parameters such as contact time, aqueous phase pH, content of phase-formation components of NaNO 3 and the ionic liquid have been investigated systematically. It is shown that under optimal conditions, the extraction efficiency of neodymium (III) is as high as 99.7%, and neodymium (III) can be selectively separated from cobalt (II) and nickel (II) with a separation factor of 10 3 . After extraction, neodymium (III) can be stripped from the IL-rich phase by using dilute aqueous sodium oxalate, and the ILs can be quantitatively recovered and reused in the next extraction process. Since [P 4444 ][NO 3 ] works as one of the components of the ATPS and the extractant for the neodymium, no organic diluent, extra etractant and fluorinated ILs are used in the separation process. Thus, the strategy described here shows potential in green separation of neodymium from cobalt and nickel by using simple IL-based aqueous two-phase system. Copyright © 2018 Elsevier B.V. All rights reserved.

Microtubules as platforms for probing liquid-liquid phase separation in cells: application to RNA-binding proteins.

PubMed

Maucuer, Alexandre; Desforges, Bénédicte; Joshi, Vandana; Boca, Mirela; Kretov, Dmitry; Hamon, Loic; Bouhss, Ahmed; Curmi, Patrick A; Pastré, David

2018-05-04

Liquid-liquid phase separation enables compartmentalization of biomolecules in cells, notably RNA and associated proteins in the nucleus. Besides critical functions in RNA processing, there is a major interest in deciphering the molecular mechanisms of compartmentalization orchestrated by RNA-binding proteins such as TDP-43 and FUS due to their link to neuron diseases. However, tools for probing compartmentalization in cells are lacking. Here we developed a method to analyze the mixing:demixing of two different phases in a cellular context. The principle is the following: mRNA-binding proteins are confined on microtubules and quantitative parameters defining their spatial segregation are measured along the microtubule network. Through this approach, we found that four mRNA binding proteins, HuR, G3BP1, TDP-43 and FUS form mRNA-rich liquid-like compartments on microtubules. TDP-43 is partly miscible with FUS but immiscible with either HuR or G3BP1. We also demonstrate that mRNA is essential to capture the mixing:demixing behavior of RNA-binding proteins in cells. Altogether we show that microtubules can be used as platforms to understand the mechanisms underlying liquid-liquid phase separation and their deregulation in human diseases. © 2018. Published by The Company of Biologists Ltd.

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.

Computation of Phase Equilibria, State Diagrams and Gas/Particle Partitioning of Mixed Organic-Inorganic Aerosols

NASA Astrophysics Data System (ADS)

Zuend, A.; Marcolli, C.; Peter, T.

2009-04-01

The chemical composition of organic-inorganic aerosols is linked to several processes and specific topics in the field of atmospheric aerosol science. Photochemical oxidation of organics in the gas phase lowers the volatility of semi-volatile compounds and contributes to the particulate matter by gas/particle partitioning. Heterogeneous chemistry and changes in the ambient relative humidity influence the aerosol composition as well. Molecular interactions between condensed phase species show typically non-ideal thermodynamic behavior. Liquid-liquid phase separations into a mainly polar, aqueous and a less polar, organic phase may considerably influence the gas/particle partitioning of semi-volatile organics and inorganics (Erdakos and Pankow, 2004; Chang and Pankow, 2006). Moreover, the phases present in the aerosol particles feed back on the heterogeneous, multi-phase chemistry, influence the scattering and absorption of radiation and affect the CCN ability of the particles. Non-ideal thermodynamic behavior in mixtures is usually described by an expression for the excess Gibbs energy, enabling the calculation of activity coefficients. We use the group-contribution model AIOMFAC (Zuend et al., 2008) to calculate activity coefficients, chemical potentials and the total Gibbs energy of mixed organic-inorganic systems. This thermodynamic model was combined with a robust global optimization module to compute potential liquid-liquid (LLE) and vapor-liquid-liquid equilibria (VLLE) as a function of particle composition at room temperature. And related to that, the gas/particle partitioning of semi-volatile components. Furthermore, we compute the thermodynamic stability (spinodal limits) of single-phase solutions, which provides information on the process type and kinetics of a phase separation. References Chang, E. I. and Pankow, J. F.: Prediction of activity coefficients in liquid aerosol particles containing organic compounds, dissolved inorganic salts, and water - Part 2: Consideration of phase separation effects by an XUNIFAC model, Atmos. Environ., 40, 6422-6436, 2006. Erdakos, G. B. and Pankow, J. F.: Gas/particle partitioning of neutral and ionizing compounds to single- and multi-phase aerosol particles. 2. Phase separation in liquid particulate matter containing both polar and low-polarity organic compounds, Atmos. Environ., 38, 1005-1013, 2004. Zuend, A., Marcolli, C., Luo, B. P., and Peter, T.: A thermodynamic model of mixed organic-inorganic aerosols to predict activity coefficients, Atmos. Chem. Phys., 8, 4559-4593, 2008.

Liquid-liquid phase separation in internally mixed magnesium sulfate/glutaric acid particles

NASA Astrophysics Data System (ADS)

Wu, Feng-Min; Wang, Xiao-Wei; Jing, Bo; Zhang, Yun-Hong; Ge, Mao-Fa

2018-04-01

The confocal Raman microscopy is utilized to investigate the liquid-liquid phase separation (LLPS) of mixed magnesium sulfate/glutaric acid (MgSO4/GA) droplets deposited on a hydrophobic polytetrafluoroethylene (PTFE) substrate and a hydrophilic quartz substrate. Raman spectra collected from different regions of the mixed droplets provide detailed information of component distributions for MgSO4 and GA. During the dehydration process, the MgSO4/GA mixed particles show the initial liquid-liquid phase separation between 85% and 80% relative humidity (RH) on both the hydrophobic and hydrophilic substrates. For the droplets deposited on the two substrates, the inner phase of droplets is dominated by aqueous MgSO4, which is surrounded by a rich GA organic layer due to the surface tension effects. In addition, the crystallization of GA could be observed in the organic aqueous phase while it is inhibited in the inner MgSO4 phase due to the effects of gel formation of MgSO4 at low RH. The Raman spectra reveal that with decreasing RH the morphology of the mixed droplet evolves from a uniform droplet to the structure of LLPS with the GA crystallizing in the outer layer and MgSO4 gel formed in the inner phase. These findings contribute to the further understanding of the role of interactions between inorganic salts and organic acids on the morphological evolution and environmental effects of atmospheric aerosols under ambient RH conditions.

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.

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.

A search for the prewetting line. [in binary liquid system at vapor-liquid interface

NASA Technical Reports Server (NTRS)

Schmidt, J. W.; Moldover, M. R.

1986-01-01

This paper describes efforts to locate the prewetting line in a binary liquid system (isopropanol-perfluoromethylcyclohexane) at the vapor-liquid interface. Tight upper bounds were placed on the temperature separation (0.2 K) between the prewetting line and the line of bulk liquid phase separation. The prewetting line in systems at equilibrium was not detected. Experimental signatures indicative of the prewetting line occurred only in nonequilibrium situations. Several theories predict that the adsorption of one of the components (the fluorocarbon, in this case) at the liquid-vapor interface should increase abruptly, at a temperature sightly above the temperature at which the mixture separates into two liquid phases. A regular solution calculation indicates that this prewetting line should have been easily detectable with the instruments used in this experiment. Significant features of the experiment are: (1) low-gradient thermostatting, (2) in situ stirring, (3) precision ellipsometry from the vapor-liquid interface, (4) high resolution differential index of refraction measurements using a novel cell design, and (5) computer control.

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

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.

Normal-Phase Open Column versus Reversed-Phase High Performance Liquid Chromatography: Separation of Chlorophyll a and Chlorophyll b from their Diastereomers.

ERIC Educational Resources Information Center

Schaber, Peter M.

1985-01-01

Background information, procedures used, and typical results obtained are provided for an experiment involving the separation of chlorophyll a and chlorophyll b from their diastereomers. Reasons why the experiment can be easily integrated into most laboratory curricula where high-performance liquid chromatography capabilities exist are given. (JN)

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.

Floating liquid phase in sedimenting colloid-polymer mixtures.

PubMed

Schmidt, Matthias; Dijkstra, Marjolein; Hansen, Jean-Pierre

2004-08-20

Density functional theory and computer simulation are used to investigate sedimentation equilibria of colloid-polymer mixtures within the Asakura-Oosawa-Vrij model of hard sphere colloids and ideal polymers. When the ratio of buoyant masses of the two species is comparable to the ratio of differences in density of the coexisting bulk (colloid) gas and liquid phases, a stable "floating liquid" phase is found, i.e., a thin layer of liquid sandwiched between upper and lower gas phases. The full phase diagram of the mixture under gravity shows coexistence of this floating liquid phase with a single gas phase or a phase involving liquid-gas equilibrium; the phase coexistence lines meet at a triple point. This scenario remains valid for general asymmetric binary mixtures undergoing bulk phase separation.

APPLICATION OF A SPRAY DEPOSITION METHOD FOR REVERSED PHASE LIQUID CHROMATOGRAPHY-MASS SPECTROMETRY

EPA Science Inventory

Four coal gasification wastewater samples were analyzed for nonvolatile and polar organics by liquid chromatography-mass spectrometry (LC/MS). Samples were separated on a reverse phase liquid chromatographic column using an aqueous solvent as the eluant. A special spray depositio...

Methods for recovering a solvent from a fluid volume and methods of removing at least one compound from a nonpolar solvent

DOEpatents

Ginosar, Daniel M.; Wendt, Daniel S.; Petkovic, Lucia M.

2014-06-10

A method of removing a nonpolar solvent from a fluid volume that includes at least one nonpolar compound, such as a fat, an oil or a triglyceride, is provided. The method comprises contacting a fluid volume with an expanding gas to expand the nonpolar solvent and form a gas-expanded solvent. The gas-expanded solvent may have a substantially reduced density in comparison to the at least one nonpolar compound and/or a substantially reduced capacity to solubilize the nonpolar compound, causing the nonpolar compounds to separate from the gas-expanded nonpolar solvent into a separate liquid phase. The liquid phase including the at least one nonpolar compound may be separated from the gas-expanded solvent using conventional techniques. After separation of the liquid phase, at least one of the temperature and pressure may be reduced to separate the nonpolar solvent from the expanding gas such that the nonpolar solvent may be recovered and reused.

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.

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.

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.

High-performance liquid chromatography analysis methods developed for quantifying enzymatic esterification of flavonoids in ionic liquids.

PubMed

Lue, Bena-Marie; Guo, Zheng; Xu, Xuebing

2008-07-11

Methods using reversed-phase high-performance liquid chromatography (RP-HPLC) with ELSD were investigated to quantify enzymatic reactions of flavonoids with fatty acids in the presence of diverse room temperature ionic liquids (RTILs). A buffered salt (preferably triethylamine-acetate) was found essential for separation of flavonoids from strongly polar RTILs, whereby RTILs were generally visible as two major peaks identified based on an ion-pairing/exchanging hypothesis. C8 and C12 stationary phases were optimal while mobile phase pH (3-7) had only a minor influence on separation. The method developed was successfully applied for primary screening of RTILs (>20), with in depth evaluation of substrates in 10 RTILs, for their evaluation as reaction media.

Pressure-Induced Dissolution and Reentrant Formation of Condensed, Liquid-Liquid Phase-Separated Elastomeric α-Elastin.

PubMed

Cinar, Hasan; Cinar, Süleyman; Chan, Hue Sun; Winter, Roland

2018-05-08

We investigated the combined effects of temperature and pressure on liquid-liquid phase separation (LLPS) phenomena of α-elastin up to the multi-kbar regime. FT-IR spectroscopy, CD, UV/Vis absorption, phase-contrast light and fluorescence microscopy techniques were employed to reveal structural changes and mesoscopic phase states of the system. A novel pressure-induced reentrant LLPS was observed in the intermediate temperature range. A molecular-level picture, in particular on the role of hydrophobic interactions, hydration, and void volume in controlling LLPS phenomena is presented. The potential role of the LLPS phenomena in the development of early cellular compartmentalization is discussed, which might have started in the deep sea, where pressures up to the kbar level are encountered. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

An Efficient Strategy Based on Liquid-Liquid Extraction with Three-Phase Solvent System and High Speed Counter-Current Chromatography for Rapid Enrichment and Separation of Epimers of Minor Bufadienolide from Toad Meat.

PubMed

Zou, Denglang; Zhu, Xuelin; Zhang, Fan; Du, Yurong; Ma, Jianbin; Jiang, Renwang

2018-01-31

This study presents an efficient strategy based on liquid-liquid extraction with three-phase solvent system and high speed counter-current chromatography for rapid enrichment and separation of epimers of minor bufadienolide from toad meat. The reflux extraction conditions were optimized by response surface methodology first, and a novel three-phase solvent system composed of n-hexane/methyl acetate/acetonitrile/water (3:6:5:5, v/v) was developed for liquid-liquid extraction of the crude extract. This integrative extraction process could enrich minor bufadienolide from complex matrix efficiently and minimize the loss of minor targets induced by repeated extraction with different kinds of organic solvents occurring in the classical liquid two-phase extraction. As a result, four epimers of minor bufadienolide were greatly enriched in the middle phase and total content of these epimers of minor bufadienolide was increased from 3.25% to 46.23%. Then, the enriched four epimers were separated by HSCCC with a two-phase solvent system composed of chloroform/methanol/water (4:2:2, v/v) successfully. Furthermore, we tested Na + ,K + -ATPase (NKA) inhibitory effect of the four epimers. 3β-Isomers of bufadienolide showed stronger (>8-fold) inhibitory activity than 3α-isomers. The characterization of minor bufadienolide in toad meat and their significant difference of inhibitory effect on NKA would promote the further quantitative analysis and safety evaluation of toad meat as a food source.

Control over phase separation and nucleation using a laser-tweezing potential

NASA Astrophysics Data System (ADS)

Walton, Finlay; Wynne, Klaas

2018-05-01

Control over the nucleation of new phases is highly desirable but elusive. Even though there is a long history of crystallization engineering by varying physicochemical parameters, controlling which polymorph crystallizes or whether a molecule crystallizes or forms an amorphous precipitate is still a poorly understood practice. Although there are now numerous examples of control using laser-induced nucleation, the absence of physical understanding is preventing progress. Here we show that the proximity of a liquid-liquid critical point or the corresponding binodal line can be used by a laser-tweezing potential to induce concentration gradients. A simple theoretical model shows that the stored electromagnetic energy of the laser beam produces a free-energy potential that forces phase separation or triggers the nucleation of a new phase. Experiments in a liquid mixture using a low-power laser diode confirm the effect. Phase separation and nucleation using a laser-tweezing potential explains the physics behind non-photochemical laser-induced nucleation and suggests new ways of manipulating matter.

Recent advances in liquid-phase separations for clinical metabolomics.

PubMed

Kohler, Isabelle; Giera, Martin

2017-01-01

Over the last decades, several technological improvements have been achieved in liquid-based separation techniques, notably, with the advent of fully porous sub-2 μm particles and superficially porous sub-3 μm particles, the comeback of supercritical fluid chromatography, and the development of alternative chromatographic modes such as hydrophilic interaction chromatography. Combined with mass spectrometry, these techniques have demonstrated their added value, substantially increasing separation efficiency, selectivity, and speed of analysis. These benefits are essential in modern clinical metabolomics typically involving the study of large-scale sample cohorts and the analysis of thousands of metabolites showing extensive differences in physicochemical properties. This review presents a brief overview of the recent developments in liquid-phase separation sciences in the context of clinical metabolomics, focusing on increased throughput as well as metabolite coverage. Relevant metabolomics applications highlighting the benefits of ultra-high performance liquid chromatography, core-shell technology, high-temperature liquid chromatography, capillary electrophoresis, supercritical fluid chromatography, and hydrophilic interaction chromatography are discussed. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Application of ionic liquids in liquid chromatography and electrodriven separation.

PubMed

Huang, Yi; Yao, Shun; Song, Hang

2013-08-01

Ionic liquids (ILs) are salts in the liquid state at ambient temperature, which are nonvolatile, nonflammable with high thermal stability and dissolve easily for a wide range of inorganic and organic materials. As a kind of potential green solvent, they show high efficiency and selectivity in the field of separation research, especially in instrumental analysis. Thus far, ILs have been successfully applied by many related researchers in high-performance liquid chromatography and capillary electrophoresis as chromatographic stationary phases, mobile phase additives or electroosmotic flow modifiers. This paper provides a detailed review of these applications in the study of natural products, foods, drugs and other fine chemicals. Furthermore, the prospects of ILs in liquid chromatographic and electrodriven techniques are discussed.

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.

Phase Separation and Crystallization of Hemoglobin C in Transgenic Mouse and Human Erythrocytes

PubMed Central

Canterino, Joseph E.; Galkin, Oleg; Vekilov, Peter G.; Hirsch, Rhoda Elison

2008-01-01

Individuals expressing hemoglobin C (β6 Glu→Lys) present red blood cells (RBC) with intraerythrocytic crystals that form when hemoglobin (Hb) is oxygenated. Our earlier in vitro liquid-liquid (L-L) phase separation studies demonstrated that liganded HbC exhibits a stronger net intermolecular attraction with a longer range than liganded HbS or HbA, and that L-L phase separation preceded and enhanced crystallization. We now present evidence for the role of phase separation in HbC crystallization in the RBC, and the role of the RBC membrane as a nucleation center. RBC obtained from both human homozygous HbC patients and transgenic mice expressing only human HbC were studied by bright-field and differential interference contrast video-enhanced microscopy. RBC were exposed to hypertonic NaCl solution (1.5–3%) to induce crystallization within an appropriate experimental time frame. L-L phase separation occurred inside the RBC, which in turn enhanced the formation of intraerythrocytic crystals. RBC L-L phase separation and crystallization comply with the thermodynamic and kinetics laws established through in vitro studies of phase transformations. This is the first report, to the best of our knowledge, to capture a temporal view of intraerythrocytic HbC phase separation, crystal formation, and dissolution. PMID:18621841

Selective extraction and separation of oxymatrine from Sophora flavescens Ait. extract by silica-confined ionic liquid.

PubMed

Bi, Wentao; Tian, Minglei; Row, Kyung Ho

2012-01-01

This study highlighted the application of a two-stepped extraction method for extraction and separation of oxymatrine from Sophora flavescens Ait. extract by utilizing silica-confined ionic liquids as sorbent. The optimized silica-confined ionic liquid was firstly mixed with plant extract to adsorb oxymatrine. Simultaneously, some interference, such as matrine, was removed. The obtained suspension was then added to a cartridge for solid phase extraction. Through these two steps, target compound was adequately separated from interferences with 93.4% recovery. In comparison with traditional solid phase extraction, this method accelerates loading and reduces the use of organic solvents during washing. Moreover, the optimization of loading volume was simplified as optimization of solid/liquid ratio. Copyright © 2011 Elsevier B.V. All rights reserved.

Highly efficient peptide separations in proteomics. Part 2: bi- and multidimensional liquid-based separation techniques.

PubMed

Sandra, Koen; Moshir, Mahan; D'hondt, Filip; Tuytten, Robin; Verleysen, Katleen; Kas, Koen; François, Isabelle; Sandra, Pat

2009-04-15

Multidimensional liquid-based separation techniques are described for maximizing the resolution of the enormous number of peptides generated upon tryptic digestion of proteomes, and hence, reduce the spatial and temporal complexity of the sample to a level that allows successful mass spectrometric analysis. This review complements the previous contribution on unidimensional high performance liquid chromatography (HPLC). Both chromatography and electrophoresis will be discussed albeit with reversed-phase HPLC (RPLC) as the final separation dimension prior to MS analysis.

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.

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.

Separations of corticosteroids using electrochemically modulated liquid chromatography: Selectivity enhancements at a porous graphitic carbon stationary phase

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

Ting, E.Y.; Porter, M.D.

Electrochemically modulated liquid chromatography has been applied to the separation of a mixture of structurally similar corticosteroids (i.e., prednisone, prednisolone, cortisone, and hydrocortisone) using a porous graphitic carbon stationary phase. Changes in the voltage applied to the column markedly affected the efficiency as well as the elution order of the separation, with the mixture fully resolved at large negative values of applied potential. Mechanistic aspects in terms of the influence of changes in the applied voltage on the extent of the interactions between these analytes and the stationary phase are briefly discussed. 19 refs., 2 figs.

Separation of aqueous two-phase polymer systems in microgravity

NASA Technical Reports Server (NTRS)

Vanalstine, J. M.; Harris, J. M.; Synder, S.; Curreri, P. A.; Bamberger, S. B.; Brooks, D. E.

1984-01-01

Phase separation of polymer systems in microgravity is studied in aircraft flights to prepare shuttle experiments. Short duration (20 sec) experiments demonstrate that phase separation proceeds rapidly in low gravity despite appreciable phase viscosities and low liquid interfacial tensions (i.e., 50 cP, 10 micro N/m). Ostwald ripening does not appear to be a satisfactory model for the phase separation mechanism. Polymer coated surfaces are evaluated as a means to localize phases separated in low gravity. Contact angle measurements demonstrate that covalently coupling dextran or PEG to glass drastically alters the 1-g wall wetting behavior of the phases in dextran-PEG two phase systems.

Metastability Gap in the Phase Diagram of Monoclonal IgG Antibody.

PubMed

Rowe, Jacob B; Cancel, Rachel A; Evangelous, Tyler D; Flynn, Rhiannon P; Pechenov, Sergei; Subramony, J Anand; Zhang, Jifeng; Wang, Ying

2017-10-17

Crystallization of IgG antibodies has important applications in the fields of structural biology, biotechnology, and biopharmaceutics. However, a rational approach to crystallize antibodies is still lacking. In this work, we report a method to estimate the solubility of antibodies at various temperatures. We experimentally determined the full phase diagram of an IgG antibody. Using the full diagram, we examined the metastability gaps, i.e., the distance between the crystal solubility line and the liquid-liquid coexistence curve, of IgG antibodies. By comparing our results to the partial phase diagrams of other IgGs reported in literature, we found that IgG antibodies have similar metastability gaps. Thereby, we present an equation with two phenomenological parameters to predict the approximate location of the solubility line of IgG antibodies with respect to their liquid-liquid coexistence curves. We have previously shown that the coexistence curve of an antibody solution can be readily determined by the polyethylene glycol-induced liquid-liquid phase separation method. Combining the polyethylene glycol-induced liquid-liquid phase separation measurements and the phenomenological equation in this article, we provide a general and practical means to predict the thermodynamic conditions for crystallizing IgG antibodies in the solution environments of interest. Copyright © 2017 Biophysical Society. Published by Elsevier Inc. All rights reserved.

[Advances of poly (ionic liquid) materials in separation science].

PubMed

Liu, Cuicui; Guo, Ting; Su, Rina; Gu, Yuchen; Deng, Qiliang

2015-11-01

Ionic liquids, as novel ionization reagents, possess beneficial characteristics including good solubility, conductivity, thermal stability, biocompatibility, low volatility and non-flammability. Ionic liquids are attracting a mass of attention of analytical chemists. Poly (ionic liquid) materials have common performances of ionic liquids and polymers, and have been successfully applied in separation science area. In this paper, we discuss the interaction mechanisms between the poly(ionic liquid) materials and analytes including hydrophobic/hydrophilic interactions, hydrogen bond, ion exchange, π-π stacking and electrostatic interactions, and summarize the application advances of the poly(ionic liquid) materials in solid phase extraction, chromatographic separation and capillary electrophoresis. At last, we describe the future prospect of poly(ionic liquid) materials.

Methylammonium formate as a mobile phase modifier for reversed-phase liquid chromatography

PubMed Central

Grossman, Shau; Danielson, Neil D.

2009-01-01

Although alkylammonium ionic liquids such as ethylammonium nitrate and ethylammonium formate have been used as mobile phase “solvents” for liquid chromatography (LC), we have shown that methylammonium formate (MAF), in part because of its lower viscosity, can be an effective replacement for methanol (MeOH) in reversed-phase LC. Plots of log retention factor versus the fraction of MeOH and MAF in the mobile phase indicate quite comparable solvent strength slope values of 2.50 and 2.05, respectively. Using a polar endcapped C18 column, furazolidone and nitrofurantoin using 20% MAF-80% water could be separated in 22 min but no baseline separation was possible using MeOH as the modifier, even down to 10%. Suppression of silanol peak broadening effects by MAF is important permitting a baseline separation of pyridoxine, thiamine, and nicotinamide using 5% MAF-95% water at 0.7 mL/min. Using 5% MeOH-95% water, severe peak broadening for thiamine is evident. The compatibility of MAF as a mobile phase modifer for LC with mass spectrometry detection of water soluble vitamins is also shown. PMID:18849044

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

Synthesis of monodisperse silica microspheres and modification with diazoresin for mixed-mode ultra high performance liquid chromatography separations.

PubMed

Cong, Hailin; Yu, Bing; Tian, Chao; Zhang, Shuai; Yuan, Hua

2017-11-01

Monodisperse silica particles with average diameters of 1.9-2.9 μm were synthesized by a modified Stöber method, in which tetraethyl orthosilicate was continuously supplied to the reaction mixture containing KCl electrolyte, water, ethanol, and ammonia. The obtained silica particles were modified by self-assembly with positively charged photosensitive diazoresin on the surface. After treatment with ultraviolet light, the ionic bonding between silica and diazoresin was converted into covalent bonding through a unique photochemistry reaction of diazoresin. Depending on the chemical structure of diazoresin and mobile phase composition, the diazoresin-modified silica stationary phase showed different separation mechanisms, including reversed phase and hydrophilic interactions. Therefore, a variety of baseline separation of benzene analogues and organic acids was achieved by using the diazoresin-modified silica particles as packing materials in ultra high performance liquid chromatography. According to the π-π interactional difference between carbon rings of fullerenes and benzene rings of diazoresin, C 60 and C 70 were also well separated by ultra-high performance liquid chromatography. Because it has a small size, the ∼2.5 μm monodisperse diazoresin-modified silica stationary phase shows ultra-high efficiency compared with the commercial C 18 -silica high-performance liquid chromatography stationary phase with average diameters of ∼5 μm. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Predicting glass-to-glass and liquid-to-liquid phase transitions in supercooled water using classical nucleation theory

NASA Astrophysics Data System (ADS)

Tournier, Robert F.

2018-01-01

Glass-to-glass and liquid-to-liquid phase transitions are observed in bulk and confined water, with or without applied pressure. They result from the competition of two liquid phases separated by an enthalpy difference depending on temperature. The classical nucleation equation of these phases is completed by this quantity existing at all temperatures, a pressure contribution, and an enthalpy excess. This equation leads to two homogeneous nucleation temperatures in each liquid phase; the first one (Tn- below Tm) being the formation temperature of an "ordered" liquid phase and the second one corresponding to the overheating temperature (Tn+ above Tm). Thermodynamic properties, double glass transition temperatures, sharp enthalpy and volume changes are predicted in agreement with experimental results. The first-order transition line at TLL = 0.833 × Tm between fragile and strong liquids joins two critical points. Glass phase above Tg becomes "ordered" liquid phase disappearing at TLL at low pressure and at Tn+ = 1.302 × Tm at high pressure.

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.

Phosphorylation-mediated RNA/peptide complex coacervation as a model for intracellular liquid organelles

NASA Astrophysics Data System (ADS)

Aumiller, William M.; Keating, Christine D.

2016-02-01

Biological cells are highly organized, with numerous subcellular compartments. Phosphorylation has been hypothesized as a means to control the assembly/disassembly of liquid-like RNA- and protein-rich intracellular bodies, or liquid organelles, that lack delimiting membranes. Here, we demonstrate that charge-mediated phase separation, or complex coacervation, of RNAs with cationic peptides can generate simple model liquid organelles capable of reversibly compartmentalizing biomolecules. Formation and dissolution of these liquid bodies was controlled by changes in peptide phosphorylation state using a kinase/phosphatase enzyme pair. The droplet-generating phase transition responded to modification of even a single serine residue. Electrostatic interactions between the short cationic peptides and the much longer polyanionic RNAs drove phase separation. Coacervates were also formed on silica beads, a primitive model for localization at specific intracellular sites. This work supports phosphoregulation of complex coacervation as a viable mechanism for dynamic intracellular compartmentalization in membraneless organelles.

Study of Separation and Identification of the Active Ingredients in Gardenia jasminoides Ellis Based on a Two-Dimensional Liquid Chromatography by Coupling Reversed Phase Liquid Chromatography and Hydrophilic Interaction Liquid Chromatography.

PubMed

Zhou, Xuan; Chen, Cen; Ye, Xiaolan; Song, Fenyun; Fan, Guorong; Wu, Fuhai

2017-01-01

In this paper, by coupling reversed phase liquid chromatography (RPLC) and hydrophilic interaction liquid chromatography (HILIC), a two-dimensional liquid chromatography system was developed for separation and identification of the active ingredients in Gardenia jasminoides Ellis (GJE). By applying the semi-preparative C18 column as the first dimension and the core-shell column as the second dimension, a total of 896 peaks of GJE were separated. Among the 896 peaks, 16 active ingredients including geniposide, gardenoside, gardoside, etc. were identified by mass spectrometry analysis. The results indicated that the proposed two-dimensional RPLC/HILIC system was an effective method for the analysis of GJE and might hold a high potential to become a useful tool for analysis of other complex mixtures. © The Author 2016. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

Investigating the Retention Mechanisms of Liquid Chromatography Using Solid-Phase Extraction Cartridges

ERIC Educational Resources Information Center

O'Donnell, Mary E.; Musial, Beata A.; Bretz, Stacey Lowery; Danielson, Neil D.; Ca, Diep

2009-01-01

Liquid chromatography (LC) experiments for the undergraduate analytical laboratory course often illustrate the application of reversed-phase LC to solve a separation problem, but rarely compare LC retention mechanisms. In addition, a high-performance liquid chromatography instrument may be beyond what some small colleges can purchase. Solid-phase…

Control of ice chromatographic retention mechanism by changing temperature and dopant concentration.

PubMed

Tasaki, Yuiko; Okada, Tetsuo

2011-12-15

A liquid phase coexists with solid water ice in a typical binary system, such as NaCl-water, in the temperature range between the freezing point and the eutectic point (t(eu)) of the system. In ice chromatography with salt-doped ice as the stationary phase, both solid and liquid phase can contribute to solute retention in different fashions; that is, the solid ice surface acts as an adsorbent, while a solute can be partitioned into the liquid phase. Thus, both adsorption and partition mechanisms can be utilized for ice chromatographic separation. An important feature in this approach is that the liquid phase volume can be varied by changing the temperature and the concentration of a salt incorporated into the ice stationary phase. Thus, we can control the relative contribution from the partition mechanism in the entire retention because the liquid phase volume can be estimated from the freezing depression curve. Separation selectivity can thereby be modified. The applicability of this concept has been confirmed for the solutes of different adsorption and partition abilities. The predicted retention based on thermodynamics basically agrees well with the corresponding experimental retention. However, one important inconsistency has been found. The calculation predicts a step-like discontinuity of the solute retention at t(eu) because the phase diagram suggests that the liquid phase abruptly appears at t(eu) when the temperature increases. In contrast, the corresponding experimental plots are continuous over the wider range including the subeutectic temperatures. This discrepancy is explained by the existence of the liquid phase below t(eu). A difference between predicted and measured retention factors allows the estimation of the volume of the subeutectic liquid phase.

A Capillary-Based Static Phase Separator for Highly Variable Wetting Conditions

NASA Technical Reports Server (NTRS)

Thomas, Evan A.; Graf, John C.; Weislogel, Mark M.

2010-01-01

The invention, a static phase separator (SPS), uses airflow and capillary wetting characteristics to passively separate a two-phase (liquid and air) flow. The device accommodates highly variable liquid wetting characteristics. The resultant design allows for a range of wetting properties from about 0 to over 90 advancing contact angle, with frequent complete separation of liquid from gas observed when using appropriately scaled test conditions. Additionally, the design accommodates a range of air-to-liquid flow-rate ratios from only liquid flow to over 200:1 air-to-liquid flow rate. The SPS uses a helix input section with an ice-cream-cone-shaped constant area cross section (see figure). The wedge portion of the cross section is on the outer edge of the helix, and collects the liquid via centripetal acceleration. The helix then passes into an increasing cross-sectional area vane region. The liquid in the helix wedge is directed into the top of capillary wedges in the liquid containment section. The transition from diffuser to containment section includes a 90 change in capillary pumping direction, while maintaining inertial direction. This serves to impinge the liquid into the two off-center symmetrical vanes by the airflow. Rather than the airflow serving to shear liquid away from the capillary vanes, the design allows for further penetration of the liquid into the vanes by the air shear. This is also assisted by locating the air exit ports downstream of the liquid drain port. Additionally, any droplets not contained in the capillary vanes are re-entrained downstream by a third opposing capillary vane, which directs liquid back toward the liquid drain port. Finally, the dual air exit ports serve to slow the airflow down, and to reduce the likelihood of shear. The ports are stove-piped into the cavity to form an unfriendly capillary surface for a wetting fluid to carryover. The liquid drain port is located at the start of the containment region, allowing for draining the bulk fluid in a continuous circuit. The functional operation of the SPS involves introducing liquid flow (from a human body, a syringe, or other source) to the two-phase inlet while an air fan pulls on the air exit lines. The fan is operated until the liquid is fully introduced. The system is drained by negative pressure on the liquid drain lines when the SPS containment system is full.

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.

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%.

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.

A Study of the Liquid-Liquid Partitioning Process Using Reverse-Phase Liquid Chromatography: An Undergraduate Analytical Chemistry Experiment.

ERIC Educational Resources Information Center

Lochmuller, C. H.; And Others

1980-01-01

Presents an undergraduate analytical chemistry experiment that promotes an interpretation of the molecular aspects of solute partitioning, enhancing student understanding of separation science and liquid chromatography. (CS)

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.

Ionic liquid stationary phases for gas chromatography.

PubMed

Poole, Colin F; Poole, Salwa K

2011-04-01

This article provides a summary of the development of ionic liquids as stationary phases for gas chromatography beginning with early work on packed columns that established details of the retention mechanism and established working methods to characterize selectivity differences compared with molecular stationary phases through the modern development of multi-centered cation and cross-linked ionic liquids for high-temperature applications in capillary gas chromatography. Since there are many reviews on ionic liquids dealing with all aspects of their chemical and physical properties, the emphasis in this article is placed on the role of gas chromatography played in the design of ionic liquids of low melting point, high thermal stability, high viscosity, and variable selectivity for separations. Ionic liquids provide unprecedented opportunities for extending the selectivity range and temperature-operating range of columns for gas chromatography, an area of separation science that has otherwise been almost stagnant for over a decade. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Process for recovering organic components from liquid streams

DOEpatents

Blume, Ingo; Baker, Richard W.

1991-01-01

A separation process for recovering organic components from liquid streams. The process is a combination of pervaporation and decantation. In cases where the liquid stream contains the organic to be separated in dissolved form, the pervaporation step is used to concentrate the organic to a point above the solubility limit, so that a two-phase permeate is formed and then decanted. In cases where the liquid stream is a two-phase mixture, the decantation step is performed first, to remove the organic product phase, and the residue from the decanter is then treated by pervaporation. The condensed permeate from the pervaporation unit is sufficiently concentrated in the organic component to be fed back to the decanter. The process can be tailored to produce only two streams: an essentially pure organic product stream suitable for reuse, and a residue stream for discharge or reuse.

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.

Fluid flow in solidifying monotectic alloys

NASA Technical Reports Server (NTRS)

Ecker, A.; Frazier, D. O.; Alexander, J. Iwan D.

1989-01-01

Use of a two-wavelength holographic technique results in a simultaneous determination of temperature and composition profiles during directional solidification in a system with a miscibility gap. The relationships among fluid flow, phase separation, and mass transport during the solidification of the monotectic alloy are discussed. The primary sources of fluid motion in this system are buoyancy and thermocapillary forces. These forces act together when phase separation results in the formation of droplets (this occurs at the solid-liquid interface and in the bulk melt). In the absence of phase separation, buoyancy results from density gradients related to temperature and compositional gradients in the single-phase bulk melt. The effects of buoyancy are especially evident in association with water- or ethanol-rich volumes created at the solid-liquid growth interface.

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.

Recent development of ionic liquid stationary phases for liquid chromatography.

PubMed

Shi, Xianzhe; Qiao, Lizhen; Xu, Guowang

2015-11-13

Based on their particular physicochemical characteristics, ionic liquids have been widely applied in many fields of analytical chemistry. Many types of ionic liquids were immobilized on a support like silica or monolith as stationary phases for liquid chromatography. Moreover, different approaches were developed to bond covalently ionic liquids onto the supporting materials. The obtained ionic liquid stationary phases show multi-mode mechanism including hydrophobic, hydrophilic, hydrogen bond, anion exchange, π-π, and dipole-dipole interactions. Therefore, they could be used in different chromatographic modes including ion-exchange, RPLC, NPLC and HILIC to separate various classes of compounds. This review mainly summarizes the immobilized patterns and types of ionic liquid stationary phases, their retention mechanisms and applications in the recent five years. Copyright © 2015 Elsevier B.V. All rights reserved.

Liquid-liquid phase transition in an ionic model of silica

NASA Astrophysics Data System (ADS)

Chen, Renjie; Lascaris, Erik; Palmer, Jeremy C.

2017-06-01

Recent equation of state calculations [E. Lascaris, Phys. Rev. Lett. 116, 125701 (2016)] for an ionic model of silica suggest that it undergoes a density-driven, liquid-liquid phase transition (LLPT) similar to the controversial transition hypothesized to exist in deeply supercooled water. Here, we perform extensive free energy calculations to scrutinize the model's low-temperature phase behavior and confirm the existence of a first-order phase transition between two liquids with identical compositions but different densities. The low-density liquid (LDL) exhibits tetrahedral order, which is partially disrupted in the high-density liquid (HDL) by the intrusion of additional particles into the primary neighbor shell. Histogram reweighting methods are applied to locate conditions of HDL-LDL coexistence and the liquid spinodals that bound the two-phase region. Spontaneous liquid-liquid phase separation is also observed directly in large-scale molecular dynamics simulations performed inside the predicted two-phase region. Given its clear LLPT, we anticipate that this model may serve as a paradigm for understanding whether similar transitions occur in water and other tetrahedral liquids.

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.

Copolymer-grafted silica phase from a cation-anion monomer pair for enhanced separation in reversed-phase liquid chromatography.

PubMed

Mallik, Abul K; Qiu, Hongdeng; Takafuji, Makoto; Ihara, Hirotaka

2014-05-01

This work reports a new imidazolium and L-alanine derived copolymer-grafted silica stationary phase for ready separation of complex isomers using high-performance liquid chromatography (HPLC). For this purpose, 1-allyl-3-octadecylimidazolium bromide ([AyImC18]Br) and N-acryloyl-L-alanine sodium salt ([AAL]Na) ionic liquids (IL) monomers were synthesized. Subsequently, the bromide counteranion was exchanged with the 2-(acrylamido)propanoate organic counteranion by reacting the [AyImC18]Br with excess [AAL]Na in water. The obtained IL cation-anion monomer pair was then copolymerized on mercaptopropyl-modified silica (Sil-MPS) via a surface-initiated radical chain-transfer reaction. The selective retention behaviors of polycyclic aromatic hydrocarbons (PAHs), including some positional isomers, steroids, and nucleobases were investigated using the newly obtained Sil-poly(ImC18-AAL), and octadecyl silylated silica (ODS) was used as the reference column. Interesting results were obtained for the separation of PAHs, steroids, and nucleobases with the new organic phase. The results showed that the Sil-poly(ImC18-AAL) presented multiple noncovalent interactions, including hydrophobic, π-π, carbonyl-π, and ion-dipole interactions for the separation of PAHs and dipolar compounds. Only pure water was sufficient as the mobile phase for the separation of the nucleobases. Ten nucleosides and bases were separated, using only water as the mobile phase, within a very short time using the Sil-poly(ImC18-AAL), which is otherwise difficult to achieve using conventional hydrophobic columns such as ODS. The combination of electrostatic and hydrophobic interactions are important for the effective separation of such basic compounds without the use of any organic additive as the eluent on the Sil-poly(ImC18-AAL) column.

Evaluation of comprehensive multidimensional separations using reversed-phase, reversed-phase liquid chromatography/mass spectrometry for shotgun proteomics.

PubMed

Nakamura, Tatsuji; Kuromitsu, Junro; Oda, Yoshiya

2008-03-01

Two-dimensional liquid-chromatographic (LC) separation followed by mass spectrometric (MS) analysis was examined for the identification of peptides in complex mixtures as an alternative to widely used two-dimensional gel electrophoresis followed by MS analysis for use in proteomics. The present method involves the off-line coupling of a narrow-bore, polymer-based, reversed-phase column using an acetonitrile gradient in an alkaline mobile phase in the first dimension with octadecylsilanized silica (ODS)-based nano-LC/MS in the second dimension. After the first separation, successive fractions were acidified and dried off-line, then loaded on the second dimension column. Both columns separate peptides according to hydrophobicity under different pH conditions, but more peptides were identified than with the conventional technique for shotgun proteomics, that is, the combination of a strong cation exchange column with an ODS column, and the system was robust because no salts were included in the mobile phases. The suitability of the method for proteomics measurements was evaluated.

HPLC SEPARATION OF CHIRAL ORGANOPHOSPHORUS PESTICIDES ON POLYSACCHARIDE CHIRAL STATIONARY PHASES

EPA Science Inventory

High-performance liquid chromatographic separation of the individual enantiomers of 12 organophosphorus pesticides (OPs) were obtained on polysaccharide chiral HPLC columns using an alkane-alcohol mobile phase. The OP pesticides were crotoxyphos, dialifor, dyfonate, fenamiphos, ...

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.

Comment on "Spontaneous liquid-liquid phase separation of water".

PubMed

Limmer, David T; Chandler, David

2015-01-01

Yagasaki et al. [Phys. Rev. E 89, 020301 (2014)] present results from a molecular dynamics trajectory illustrating coarsening of ice, which they interpret as evidence of transient coexistence between two distinct supercooled phases of liquid water. We point out that neither two distinct liquids nor criticality are demonstrated in this simulation study. Instead, the illustrated trajectory is consistent with coarsening behaviors analyzed and predicted in earlier work by others.

Fluorous tagging strategy for solution-phase synthesis of small molecules, peptides and oligosaccharides

PubMed Central

Zhang, Wei

2005-01-01

The purification of reaction mixtures is a slow process in organic synthesis, especially during the production of large numbers of analogs and compound libraries. Phase-tag methods such as solid-phase synthesis and fluorous synthesis, provide efficient ways of addressing the separation issue. Fluorous synthesis employs functionalized perfluoroalkyl groups attached to substrates or reagents. The separation of the resulting fluorous molecules can be achieved using strong and selective fluorous liquid-liquid extraction, fluorous silica gel-based solid-phase extraction or high-performance liquid chromatography. Fluorous technology is a novel solution-phase method, which has the advantages of fast reaction times in homogeneous environments, being readily adaptable to literature conditions, having easy intermediate analysis, and having flexibility in reaction scale and scope. In principle, any synthetic methods that use a solid-support could be conducted in solution-phase by replacing the polymer linker with a corresponding fluorous tag. This review summarizes the progress of fluorous tags in solution-phase synthesis of small molecules, peptides and oligosaccharides. PMID:15595439

Determination of capsaicinoids in topical cream by liquid-liquid extraction and liquid chromatography.

PubMed

Kaale, Eliangiringa; Van Schepdael, Ann; Roets, Eugène; Hoogmartens, Jos

2002-11-07

A reversed-phase liquid chromatography (LC) method has been developed, optimised and validated for the separation and quantitation of capsaicin (CP) and dihydrocapsaicin (DHCP) in a topical cream formulation. Sample preparation involves liquid-liquid extraction prior to LC analysis. The method uses a Hypersil C(18) BDS, 5 micrometer, 250x4.6 mm I.D. column maintained at 35 degrees C. The mobile phase comprises methanol, water, acetonitrile (ACN) and acetic acid (47:42:10:1, v/v/v/v) at a flow rate of 1.0 ml/min. Robustness was evaluated by performing a central composite face-centred design (CCF) experiment. The method shows good selectivity, linearity, sensitivity and repeatability. The conditions allow the separation and quantitation of CP and DHCP without interference from the other substances contained in the cream.

pH Variance in Aerosols Undergoing Liquid-Liquid Phase Separation

NASA Astrophysics Data System (ADS)

Eddingsaas, N. C.; Dallemagne, M.; Huang, X.

2014-12-01

The water content of aerosols is largely governed by relative humidity (RH). As the relative humidity decreases, and thus the water content of aerosols, a number of processes occur including the shrinking of aerosols, the increase in concentration of components, and potentially the formation of liquid liquid phase separation (llps) due to the salting out of inorganic salts. The most ubiquitous salt in atmospheric aerosols is ammonium sulfate which results in many aerosols to be at least mildly acidic. However, during llps, the pH of the different phases is not necessarily the same. Many reactions that take place within atmospheric aerosols are acid catalyzed so a better understanding of the pH of the individual phases as well as the interface between the phases is important to understanding aerosol processing and aging. Through the use of pH sensitive dyes and confocal microscopy we have directly measured the pH of micron sized model aerosols during high RH where the aerosols are in a single phase, at intermediate while the aerosols are in llps, and low RH where the aerosols consist of one liquid phase and one solid phase. We will discuss the variation in RH during these different phase states in the presence and absence of excess sulfuric acid. We will also discuss how this variation in pH affects aging of aerosols.

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...

Cryogenic test of the 4 K / 2 K insert for the ARIEL e-Linac cryomodule

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

Laxdal, R. E.; Ma, Y.; Harmer, P.

2014-01-29

The ARIEL project at TRIUMF requires a 50 MeV superconducting electron linac consisting of five nine cell 1.3 GHz cavities divided into three cryomodules with one, two and two cavities in each module respectively. LHe is distributed in parallel to each module at 4 K and at ∼1.2 bar. Each module has a cryogenic insert on board that receives the 4 K liquid and produces 2 K into a cavity phase separator. The module combines a 4 K phase separator, a plate and fin heat exchanger from DATE and a J-T valve expanding into the 2 K phase separator. Themore » unit also supplies 4 K liquid to thermal intercepts in the module in siphon loops that return the vaporized liquid to the 4 K reservoir. For testing purposes the unit is outfitted with a dummy 2 K phase separator and thermal intercepts with variable heaters that mimic the final heat loads in order to test the cryogenic performance. The design of the 4 K / 2 K insert, the results of the cold tests and a summary of the test infrastructure including cryogenics services will be presented.« less

Use of frit-disc crucibles for routine and exploratory solution growth of single crystalline samples

DOE PAGES

Canfield, Paul C.; Kong, Tai; Kaluarachchi, Udhara S.; ...

2016-01-05

Solution growth of single crystals from high temperature solutions often involves the separation of residual solution from the grown crystals. For many growths of intermetallic compounds, this separation has historically been achieved with the use of plugs of silica wool. Whereas this is generally efficient in a mechanical sense, it leads to a significant contamination of the decanted liquid with silica fibres. In this paper, we present a simple design for frit-disc alumina crucible sets that has made their use in the growth single crystals from high temperature solutions both simple and affordable. An alumina frit-disc allows for the cleanmore » separation of the residual liquid from the solid phase. This allows for the reuse of the decanted liquid, either for further growth of the same phase, or for subsequent growth of other, related phases. In this article, we provide examples of the growth of isotopically substituted TbCd 6 and icosahedral i-RCd quasicrystals, as well as the separation of (i) the closely related Bi 2Rh 3S 2 and Bi 2Rh 3.5S 2 phases and (ii) and PrZn 11 and PrZn 17.« less

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.

Phase equilibrium measurements on nine binary mixtures

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

Wilding, W.V.; Giles, N.F.; Wilson, L.C.

1996-11-01

Phase equilibrium measurements have been performed on nine binary mixtures. The PTx method was used to obtain vapor-liquid equilibrium data for the following systems at two temperatures each: (aminoethyl)piperazine + diethylenetriamine; 2-butoxyethyl acetate + 2-butoxyethanol; 2-methyl-2-propanol + 2-methylbutane; 2-methyl-2-propanol + 2-methyl-2-butene; methacrylonitrile + methanol; 1-chloro-1,1-difluoroethane + hydrogen chloride; 2-(hexyloxy)ethanol + ethylene glycol; butane + ammonia; propionaldehyde + butane. Equilibrium vapor and liquid phase compositions were derived form the PTx data using the Soave equation of state to represent the vapor phase and the Wilson or the NRTL activity coefficient model to represent the liquid phase. A large immiscibility region existsmore » in the butane + ammonia system at 0 C. Therefore, separate vapor-liquid-liquid equilibrium measurements were performed on this system to more precisely determine the miscibility limits and the composition of the vapor phase in equilibrium with the two liquid phases.« less

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.

The Separation and Identification of Straight Chain Hydrocarbons: An Experiment Using Gas-Liquid Chromatography.

ERIC Educational Resources Information Center

Benson, G. A.

1982-01-01

An experiment using gas-liquid chromatography is discussed, introducing the student to concept of dead volume and its measurement, idea and use of an internal reference compound, and to linear relationship existing between measurements of a separation on two different stationary phases. (Author/SK)

Separation of four flavonol glycosides from Solanum rostratum Dunal using aqueous two-phase flotation followed by preparative high-performance liquid chromatography.

PubMed

Chang, Lin; Shao, Qian; Xi, Xingjun; Chu, Qiao; Wei, Yun

2017-02-01

Aqueous two-phase flotation followed by preparative high-performance liquid chromatography was used to separate four flavonol glycosides from Solanum rostratum Dunal. In the aqueous two-phase flotation section, the effects of sublation solvent, solution pH, (NH 4 ) 2 SO 4 concentration in aqueous solution, cosolvent, N 2 flow rate, flotation time, and volumes of the polyethylene glycol phase on the recovery were investigated in detail, and the optimal conditions were selected: 50 wt% polyethylene glycol 1000 ethanol solvent as the flotation solvent, pH 4, 350 g/L of (NH 4 ) 2 SO 4 concentration in aqueous phase, 40 mL/min of N 2 flow rate, 30 min of flotation time, 10.0 mL of flotation solvent volume, and two times. After aqueous two-phase flotation concentration, the flotation products were purified by preparative high-performance liquid chromatography. The purities of the final products A and B were 98.1 and 99.0%. Product B was the mixture of three compounds based on the analysis of high-performance liquid chromatography at the temperature of 10°C, while product A was hyperoside after the identification by nuclear magnetic resonance. Astragalin, 3'-O-methylquercetin 3-O-β-d-galactopyranoside, and 3'-O-methylquercetin 3-O-β-d-glucopyranoside were obtained with the purity of 93.8, 97.1, and 99.2%, respectively, after the further separation of product B using preparative high-performance liquid chromatography. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Density functional theory of gas-liquid phase separation in dilute binary mixtures

NASA Astrophysics Data System (ADS)

Okamoto, Ryuichi; Onuki, Akira

2016-06-01

We examine statics and dynamics of phase-separated states of dilute binary mixtures using density functional theory. In our systems, the difference of the solvation chemical potential between liquid and gas Δ {μ\\text{s}} (the Gibbs energy of transfer) is considerably larger than the thermal energy {{k}\\text{B}}T for each solute particle and the attractive interaction among the solute particles is weaker than that among the solvent particles. In these conditions, the saturated vapor pressure increases by {{k}\\text{B}}Tn2\\ell\\exp ≤ft(Δ {μ\\text{s}}/{{k}\\text{B}}T\\right) , where n2\\ell is the solute density added in liquid. For \\exp ≤ft(Δ {μ\\text{s}}/{{k}\\text{B}}T\\right)\\gg 1 , phase separation is induced at low solute densities in liquid and the new phase remains in gaseous states, even when the liquid pressure is outside the coexistence curve of the solvent. This explains the widely observed formation of stable nanobubbles in ambient water with a dissolved gas. We calculate the density and stress profiles across planar and spherical interfaces, where the surface tension decreases with increasing interfacial solute adsorption. We realize stable solute-rich bubbles with radius about 30 nm, which minimize the free energy functional. We then study dynamics around such a bubble after a decompression of the surrounding liquid, where the bubble undergoes a damped oscillation. In addition, we present some exact and approximate expressions for the surface tension and the interfacial stress tensor.

Liquid-liquid phase separation causes high turbidity and pressure during low pH elution process in Protein A chromatography.

PubMed

Luo, Haibin; Lee, Nacole; Wang, Xiangyang; Li, Yuling; Schmelzer, Albert; Hunter, Alan K; Pabst, Timothy; Wang, William K

2017-03-10

Turbid elution pools and high column back pressure are common during elution of monoclonal antibodies (mAbs) by acidic pH in Protein A chromatography. This phenomenon has been historically attributed to acid-induced precipitation of incorrectly folded or pH-sensitive mAbs and host cell proteins (HCPs). In this work, we propose a new mechanism that may account for some observations of elution turbidity in Protein A chromatography. We report several examples of turbidity and high column back pressure occurring transiently under a short course of neutral conditions during Protein A elution. A systematic study of three mAbs displaying this behavior revealed phase separation characterized by liquid drops under certain conditions including neutral pH, low ionic strength, and high protein concentration. These liquid droplets caused solution turbidity and exhibited extremely high viscosity, resulting in high column back pressure. We found out that the droplets were formed through liquid-liquid phase separation (LLPS) as a result of protein self-association. We also found multiple factors, including pH, temperature, ionic strength, and protein concentration can affect LLPS behaviors. Careful selection of process parameters during protein A elution, including temperature, flow rate, buffer, and salt can inhibit formation of a dense liquid phase, reducing both turbidity (by 90%) and column back pressure (below 20 pounds per square inch). These findings provide both mechanistic insight and practical mitigation strategies for Protein A chromatography induced LLPS. Copyright © 2017 The Author(s). Published by 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.

Electrowetting lenses for compensating phase and curvature distortion in arrayed laser systems.

PubMed

Niederriter, Robert D; Watson, Alexander M; Zahreddine, Ramzi N; Cogswell, Carol J; Cormack, Robert H; Bright, Victor M; Gopinath, Juliet T

2013-05-10

We have demonstrated a one-dimensional array of individually addressable electrowetting tunable liquid lenses that compensate for more than one wave of phase distortion across a wavefront. We report a scheme for piston control using tunable liquid lens arrays in volume-bound cavities that alter the optical path length without affecting the wavefront curvature. Liquid lens arrays with separately tunable focus or phase control hold promise for laser communication systems and adaptive optics.

Charge Transport and Phase Behavior of Imidazolium-Based Ionic Liquid Crystals from Fully Atomistic Simulations.

PubMed

Quevillon, Michael J; Whitmer, Jonathan K

2018-01-02

Ionic liquid crystals occupy an intriguing middle ground between room-temperature ionic liquids and mesostructured liquid crystals. Here, we examine a non-polarizable, fully atomistic model of the 1-alkyl-3-methylimidazolium nitrate family using molecular dynamics in the constant pressure-constant temperature ensemble. These materials exhibit a distinct "smectic" liquid phase, characterized by layers formed by the molecules, which separate the ionic and aliphatic moieties. In particular, we discuss the implications this layering may have for electrolyte applications.

A comparative evaluation of different ionic liquids for arsenic species separation and determination in wine varietals by liquid chromatography - hydride generation atomic fluorescence spectrometry.

PubMed

Castro Grijalba, Alexander; Fiorentini, Emiliano F; Martinez, Luis D; Wuilloud, Rodolfo G

2016-09-02

The application of different ionic liquids (ILs) as modifiers for chromatographic separation and determination of arsenite [As(III)], arsenate [As(V)], dimethylarsonic acid (DMA) and monomethylarsonic acid (MMA) species in wine samples, by reversed-phase high performance liquid chromatography coupled to hydride generation atomic fluorescence spectrometry detection (RP-HPLC-HG-AFS) was studied in this work. Several factors influencing the chromatographic separation of the As species, such as pH of the mobile phase, buffer solution concentration, buffer type, IL concentration and length of alkyl groups in ILs were evaluated. The complete separation of As species was achieved using a C18 column in isocratic mode with a mobile phase composed of 0.5% (v/v) 1-octyl-3-methylimidazolium chloride ([C8mim]Cl) and 5% (v/v) methanol at pH 8.5. A multivariate methodology was used to optimize the variables involved in AFS detection of As species after they were separated by HPLC. The ILs showed remarkable performance for the separation of As species, which was obtained within 18min with a resolution higher than 0.83. The limits of detection for As(III), As(V), MMA and DMA were 0.81, 0.89, 0.62 and 1.00μg As L(-1). The proposed method was applied for As speciation analysis in white and red wine samples originated from different grape varieties. Copyright © 2016 Elsevier B.V. All rights reserved.

Fully automated multifunctional ultrahigh pressure liquid chromatography system for advanced proteome analyses

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

Lee, Jung Hwa; Hyung, Seok-Won; Mun, Dong-Gi

2012-08-03

A multi-functional liquid chromatography system that performs 1-dimensional, 2-dimensional (strong cation exchange/reverse phase liquid chromatography, or SCX/RPLC) separations, and online phosphopeptides enrichment using a single binary nano-flow pump has been developed. With a simple operation of a function selection valve, which is equipped with a SCX column and a TiO2 (titanium dioxide) column, a fully automated selection of three different experiment modes was achieved. Because the current system uses essentially the same solvent flow paths, the same trap column, and the same separation column for reverse-phase separation of 1D, 2D, and online phosphopeptides enrichment experiments, the elution time information obtainedmore » from these experiments is in excellent agreement, which facilitates correlating peptide information from different experiments.« less

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.

Liquid crystalline composites toward organic photovoltaic application (Conference Presentation)

NASA Astrophysics Data System (ADS)

Shimizu, Yo; Sosa-Vargas, Lydia; Shin, Woong; Higuchi, Yumi; Itani, Hiromichi; Kawano, Koki; Dao, Quang Duy; Fujii, Akihiko; Ozaki, Masanori

2017-02-01

Liquid crystalline semiconductor is an interesting category of organic electronic materials and also has been extensively studied in terms of "Printed Electronics". For the wider diversity in research toward new applications, one can consider how to use a combination of miscibility and phase separation in liquid crystals. Here we report discotic liquid crystals in making a composite of which structural order is controlled in nano-scale toward photovoltaic applications. Discotic columnar LCs were studied on their resultant molecular order and carrier transport properties. Liquid crystals of phthalocyanine and its analogues which exhibit columnar mesomorphism with high carrier mobility (10-1 cm2/Vs) were examined with making binary phase diagrams and the correlation to carrier transport properties by TOF measurements was discussed. The shape-analogues in chemical structure shows a good miscibility even for the different lattice-type of columnar arrangement and the carrier mobility is mostly decrease except for a case of combination with a metal-free and the metal complex. For the mixtures with non-mesogenic C60 derivatives, one sees a phase-separated structure due to its immiscibility, though the columnar order is remained in a range of component ratio.Especially, in a range of the ratio, it was observed the phase separated C60 derivatives are fused into the matrix of columnar bundles, indicating C60 derivatives could be diffused in columnar arrays in molecular level.

Design of Phosphonium-Type Zwitterion as an Additive to Improve Saturated Water Content of Phase-Separated Ionic Liquid from Aqueous Phase toward Reversible Extraction of Proteins

PubMed Central

Ito, Yoritsugu; Kohno, Yuki; Nakamura, Nobuhumi; Ohno, Hiroyuki

2013-01-01

We designed phosphonium-type zwitterion (ZI) to control the saturated water content of separated ionic liquid (IL) phase in the hydrophobic IL/water biphasic systems. The saturated water content of separated IL phase, 1-butyl-3-methyimidazolium bis(trifluoromethanesulfonyl)imide, was considerably improved from 0.4 wt% to 62.8 wt% by adding N,N,N-tripentyl-4-sulfonyl-1-butanephosphonium-type ZI (P555C4S). In addition, the maximum water content decreased from 62.8 wt% to 34.1 wt% by increasing KH2PO4/K2HPO4 salt content in upper aqueous phosphate buffer phase. Horse heart cytochrome c (cyt.c) was dissolved selectively in IL phase by improving the water content of IL phase, and spectroscopic analysis revealed that the dissolved cyt.c retained its higher ordered structure. Furthermore, cyt. c dissolved in IL phase was re-extracted again from IL phase to aqueous phase by increasing the concentration of inorganic salts of the buffer solution. PMID:24013379

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.

Silica, hybrid silica, hydride silica and non-silica stationary phases for liquid chromatography.

PubMed

Borges, Endler M

2015-04-01

Free silanols on the surface of silica are the "villains", which are responsible for detrimental interactions of those compounds and the stationary phase (i.e., bad peak shape, low efficiency) as well as low thermal and chemical stability. For these reasons, we began this review describing new silica and hybrid silica stationary phases, which have reduced and/or shielded silanols. At present, in liquid chromatography for the majority of analyses, reversed-phase liquid chromatography is the separation mode of choice. However, the needs for increased selectivity and increased retention of hydrophilic bases have substantially increased the interest in hydrophilic interaction chromatography (HILIC). Therefore, stationary phases and this mode of separation are discussed. Then, non-silica stationary phases (i.e., zirconium oxide, titanium oxide, alumina and porous graphitized carbon), which afford increased thermal and chemical stability and also selectivity different from those obtained with silica and hybrid silica, are discussed. In addition, the use of these materials in HILIC is also reviewed. © Crown copyright 2014.

The role of disclinations on the organization and conductivity in liquid crystal nanocomposites

NASA Astrophysics Data System (ADS)

Martinez-Miranda, Luz J.; Romero-Hasler, P.; Meneses-Franco, A.; Soto-Bustamante, E. A.

The structure of TiO2 nanoparticles in a liquid crystal nanocomposite was found to be an oblique structure due to the alignment of the TiO2 with respect to the liquid crystals. This order is anisotropic due to the ordering of the liquid crystals. The particles are highly localized in the nanocomposite, which has consequences in the electrical percolation. We want to obtain an understanding of how the nanoparticles organize in this highly localized fashion. The nanoparticles and the liquid crystals phase separate, with the nanoparticles accumulating in the defects exhibited by the liquid crystal even after being sonicated initially. The liquid crystal is polymerized by the process of electropolymerization that takes place in the isotropic phase of the monomers. The nanoparticles are free to move away from the defects where they phase separate since the defects disappear in the isotropic. We believe the polymerization imposes a limitation in the movement of the nanoparticles. The combination of the accumulation in the disclinations, the polymerization in the isotropic and the formation of the liquid crystal unit side chains can affect the conductivity of the nanocomposite. NSF-OISE-1157589; Fondecyt Project 1130187; CONICYT scholarships 21130413 and 21090713.

Indirect ultraviolet detection of alkaline earth metal ions using an imidazolium ionic liquid as an ultraviolet absorption reagent in ion chromatography.

PubMed

Liu, Yong-Qiang; Yu, Hong

2017-04-01

A convenient and versatile method was developed for the separation and detection of alkaline earth metal ions by ion chromatography with indirect UV detection. The chromatographic separation of Mg 2+ , Ca 2+ , and Sr 2+ was performed on a carboxylic acid base cation exchange column using imidazolium ionic liquid/acid as the mobile phase, in which the imidazolium ionic liquid acted as an UV-absorption reagent. The effects of imidazolium ionic liquids, detection wavelength, acids in the mobile phase, and column temperature on the retention of Mg 2+ , Ca 2+ , and Sr 2+ were investigated. The main factors influencing the separation and detection were the background UV absorption reagent and the concentration of hydrogen ion in ion chromatography with indirect UV detection. The successful separation and detection of Mg 2+ , Ca 2+ , and Sr 2+ within 14 min were achieved using the selected chromatographic conditions, and the detection limits (S/N = 3) were 0.06, 0.12, and 0.23 mg/L, respectively. A new separation and detection method of alkaline earth metal ions by ion chromatography with indirect UV detection was developed, and the application range of ionic liquids was expanded. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Vapors-liquid phase separator. [infrared telescope heat sink

NASA Technical Reports Server (NTRS)

Frederking, T. H. K.; Brown, G. S.; Chuang, C.; Kamioka, Y.; Kim, Y. I.; Lee, J. M.; Yuan, S. W. K.

1980-01-01

The use of porous plugs, mostly with in the form of passive devices with constant area were considered as vapor-liquid phase separators for helium 2 storage vessels under reduced gravity. The incorporation of components with variable cross sectional area as a method of flow rate modification was also investigated. A particular device which uses a shutter-type system for area variation was designed and constructed. This system successfully permitted flor rate changes of up to plus or minus 60% from its mean value.

Greenhouse gas and ammonia emissions from production of compost bedding on a dairy farm.

PubMed

Fillingham, M A; VanderZaag, A C; Burtt, S; Baldé, H; Ngwabie, N M; Smith, W; Hakami, A; Wagner-Riddle, C; Bittman, S; MacDonald, D

2017-12-01

Recent developments in composting technology enable dairy farms to produce their own bedding from composted manure. This management practice alters the fate of carbon and nitrogen; however, there is little data available documenting how gaseous emissions are impacted. This study measured in-situ emissions of methane (CH 4 ), carbon dioxide (CO 2 ), nitrous oxide (N 2 O), and ammonia (NH 3 ) from an on-farm solid-liquid separation system followed by continuously-turned plug-flow composting over three seasons. Emissions were measured separately from the continuously-turned compost phase, and the compost-storage phase prior to the compost being used for cattle bedding. Active composting had low emissions of N 2 O and CH 4 with most carbon being emitted as CO 2 -C and most N emitted as NH 3 -N. Compost storage had higher CH 4 and N 2 O emissions than the active phase, while NH 3 was emitted at a lower rate, and CO 2 was similar. Overall, combining both the active composting and storage phases, the mean total emissions were 3.9×10 -2 gCH 4 kg -1 raw manure (RM), 11.3gCO 2 kg -1 RM, 2.5×10 -4 g N 2 O kg -1 RM, and 0.13g NH 3 kg -1 RM. Emissions with solid-separation and composting were compared to calculated emissions for a traditional (unseparated) liquid manure storage tank. The total greenhouse gas emissions (CH 4 +N 2 O) from solid separation, composting, compost storage, and separated liquid storage were reduced substantially on a CO 2 -equivalent basis compared to traditional liquid storage. Solid-liquid separation and well-managed composting could mitigate overall greenhouse gas emissions; however, an environmental trade off was that NH 3 was emitted at higher rates from the continuously turned composter than reported values for traditional storage. Crown Copyright © 2017. Published by Elsevier Ltd. All rights reserved.

ANALYSIS OF SELECTED PYRETHROID PESTICIDES USING REVERSE PHASE HIGH PRESSURE LIQUID CHROMATOGRAPHY/UV

EPA Science Inventory

This research was conducted in cooperation with EPA Region 4 in Athens, GA to develop a method to analyze selected pyrethroid pesticides using Reverse Phase-High Pressure Liquid Chromatography (HPLC). This HPLC method will aid researchers in separating and identifying these py...

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.

Liquid-liquid equilibria for hydrogen fluoride + 1,1-dichloro-1-fluoroethane + 1-chloro-1,1-difluoroethane at {minus}20 and 20 C

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

Kang, Y.W.; Lee, Y.Y.

1995-03-01

1,1-Dichloro-1-fluoroethane is presently under consideration as a replacement for trichlorofluoromethane, which is widely used as a foam blowing agent. 1-Chloro-1,1-difluoroethane is the major raw material for the production of poly(vinylidene fluoride). These two materials are normally manufactured by the fluorination of 1,1,1-trichloroethane or vinylidene chloride with hydrogen fluoride. A phase separator is normally used to retrieve hydrogen fluoride from the product stream. To design the phase separator, liquid-liquid equilibrium data are required. Liquid-liquid equilibria for the ternary system (hydrogen fluoride + 1,1-dichloro-1-fluoroethane + 1-chloro-1,1-difluoroethane) have been measured at {minus}20 and 20 C. The results are correlated with the NRTL model,more » and the relevant parameters are presented.« less

Separation of m-cresol from neutral oils with liquid-liquid extraction

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

Venter, D.L.; Nieuwoudt

Coal pyrolysis liquors are a major source of valuable phenolic compounds. In this study, the separation of m-cresol from neutral oils by means of liquid-liquid extraction is investigated. Liquid-liquid equilibria for the systems m-cresol + o-toluonitrile + hexane + water + tetraethylene glycol + undecane + dodecane and m-cresol + o-toluonitrile + hexane + water + tetraethylene glycol have bee determined at 313.15 K in order to evaluate the suitability of tetraethylene glycol as a high-boiling solvent for the separation of m-cresol from neutral oils. The effect of parameters such as solvent ratios on the desired separation were investigated. Thesemore » are illustrated on the basis of separation factors, percentage of feed o-toluonitrile remaining in the solvent phase, and percentage recovery of m-cresol. From the experimental results it was concluded that tetraethylene glycol is suitable for the proposed separation. The nonrandom two-liquid model fitted the experimental data satisfactorily. The model was used in the simulation of a multistage extraction column. m-Cresol recoveries of greater than 97% and m-cresol purity of greater than 99.5% were predicted.« less

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.

Fast and comprehensive analysis of secondary metabolites in cocoa products using ultra high-performance liquid chromatography directly after pressurized liquid extraction.

PubMed

Damm, Irina; Enger, Eileen; Chrubasik-Hausmann, Sigrun; Schieber, Andreas; Zimmermann, Benno F

2016-08-01

Fast methods for the extraction and analysis of various secondary metabolites from cocoa products were developed and optimized regarding speed and separation efficiency. Extraction by pressurized liquid extraction is automated and the extracts are analyzed by rapid reversed-phase ultra high-performance liquid chromatography and normal-phase high-performance liquid chromatography methods. After extraction, no further sample treatment is required before chromatographic analysis. The analytes comprise monomeric and oligomeric flavanols, flavonols, methylxanthins, N-phenylpropenoyl amino acids, and phenolic acids. Polyphenols and N-phenylpropenoyl amino acids are separated in a single run of 33 min, procyanidins are analyzed by normal-phase high-performance liquid chromatography within 16 min, and methylxanthins require only 6 min total run time. A fourth method is suitable for phenolic acids, but only protocatechuic acid was found in relevant quantities. The optimized methods were validated and applied to 27 dark chocolates, one milk chocolate, two cocoa powders and two food supplements based on cocoa extract. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Aggregation in complex triacylglycerol oils: coarse-grained models, nanophase separation, and predicted x-ray intensities

NASA Astrophysics Data System (ADS)

Quinn, Bonnie; Peyronel, Fernanda; Gordon, Tyler; Marangoni, Alejandro; Hanna, Charles B.; Pink, David A.

2014-11-01

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 componentt, 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 Δ. 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 \\lt 0.0701 u (b) transition regime, 0.0701 u≤slant Δ ≤slant 0.0916 u and (c) thick coating regime, Δ \\gt 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\\lt Δ \\lt 7.0 \\text{nm} transition regime, 7.0\\ltΔ \\lt 9.2 \\text{nm} and thick coating, Δ \\gt 9.2 \\text{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%.

Applications of the solvation parameter model in reversed-phase liquid chromatography.

PubMed

Poole, Colin F; Lenca, Nicole

2017-02-24

The solvation parameter model is widely used to provide insight into the retention mechanism in reversed-phase liquid chromatography, for column characterization, and in the development of surrogate chromatographic models for biopartitioning processes. The properties of the separation system are described by five system constants representing all possible intermolecular interactions for neutral molecules. The general model can be extended to include ions and enantiomers by adding new descriptors to encode the specific properties of these compounds. System maps provide a comprehensive overview of the separation system as a function of mobile phase composition and/or temperature for method development. The solvation parameter model has been applied to gradient elution separations but here theory and practice suggest a cautious approach since the interpretation of system and compound properties derived from its use are approximate. A growing application of the solvation parameter model in reversed-phase liquid chromatography is the screening of surrogate chromatographic systems for estimating biopartitioning properties. Throughout the discussion of the above topics success as well as known and likely deficiencies of the solvation parameter model are described with an emphasis on the role of the heterogeneous properties of the interphase region on the interpretation and understanding of the general retention mechanism in reversed-phase liquid chromatography for porous chemically bonded sorbents. Copyright © 2016 Elsevier B.V. All rights reserved.

Methods for calculation of engineering parameters for gas separation. [vapor pressure and solubility of gases in organic liquids

NASA Technical Reports Server (NTRS)

Lawson, D. D.

1979-01-01

A group additivity method is generated which allows estimation, from the structural formulas alone, of the energy of vaporization and the molar volume at 25 C of many nonpolar organic liquids. Using these two parameters and appropriate thermodynamic relations, the vapor pressure of the liquid phase and the solubility of various gases in nonpolar organic liquids are predicted. It is also possible to use the data to evaluate organic and some inorganic liquids for use in gas separation stages or liquids as heat exchange fluids in prospective thermochemical cycles for hydrogen production.

(PRESENT AT NCCU) ANALYSIS OF SELECTED PYRETHROID PESTICIDES USING REVERSE PHASE HIGH LIQUID CHROMATOGRAPHY

EPA Science Inventory

This research was conducted in cooperation with EPA Region 4 in Athens, GA to develop a method to analyze selected pyrethroid pesticides using Reverse Phase-High Pressure Liquid Chromatography (HPLC). This HPLC method will aid researchers in separating and identifying these pyre...

Nucleophosmin integrates within the nucleolus via multi-modal interactions with proteins displaying R-rich linear motifs and rRNA.

PubMed

Mitrea, Diana M; Cika, Jaclyn A; Guy, Clifford S; Ban, David; Banerjee, Priya R; Stanley, Christopher B; Nourse, Amanda; Deniz, Ashok A; Kriwacki, Richard W

2016-02-02

The nucleolus is a membrane-less organelle formed through liquid-liquid phase separation of its components from the surrounding nucleoplasm. Here, we show that nucleophosmin (NPM1) integrates within the nucleolus via a multi-modal mechanism involving multivalent interactions with proteins containing arginine-rich linear motifs (R-motifs) and ribosomal RNA (rRNA). Importantly, these R-motifs are found in canonical nucleolar localization signals. Based on a novel combination of biophysical approaches, we propose a model for the molecular organization within liquid-like droplets formed by the N-terminal domain of NPM1 and R-motif peptides, thus providing insights into the structural organization of the nucleolus. We identify multivalency of acidic tracts and folded nucleic acid binding domains, mediated by N-terminal domain oligomerization, as structural features required for phase separation of NPM1 with other nucleolar components in vitro and for localization within mammalian nucleoli. We propose that one mechanism of nucleolar localization involves phase separation of proteins within the nucleolus.

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.

A new solution to emulsion liquid membrane problems by non-Newtonian conversion

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

Skelland, A.H.P.; Meng, X.

1996-02-01

Surfactant-stabilized emulsion liquid membrane processes constitute an emerging separation technology that has repeatedly been shown to be highly suited for such diverse separation processes as metal recovery or removal from dilute aqueous solutions; separations in the food industry; removal of organic bases and acids from water; and separation of hydrocarbons. Emulsion liquid membrane separation processes remain excessively vulnerable to one or more of four major problems. Difficulties lie in developing liquid membranes that combine high levels of both stability and permeability with acceptably low levels of swelling and ease of subsequent demulsification for membrane and solute recovery. This article providesmore » a new technique for simultaneously overcoming the first three problems, while identifying physical indications that the proposed solution may have little adverse effect on the fourth problem (demulsification) and may even alleviate it. Numerous benefits of optimized conversion of the membrane phase into suitable non-Newtonian form are identified, their mechanisms outlined, and experimental verifications provided. These include increased stability, retained (or enhanced) permeability, reduced swelling, increased internal phase volume, and increased stirrer speeds. The highly favorable responsiveness of both aliphatic and aromatic membranes to the new technique is demonstrated.« less

31 CFR 561.318 - Petroleum.

Code of Federal Regulations, 2012 CFR

2012-07-01

... § 561.318 Petroleum. A mixture of hydrocarbons that exists in liquid phase in natural underground reservoirs and remains liquid at atmospheric pressure after passing through surface separating facilities...

Comment on "Spontaneous liquid-liquid phase separation of water"

NASA Astrophysics Data System (ADS)

Limmer, David T.; Chandler, David

2015-01-01

Yagasaki et al. [Phys. Rev. E 89, 020301 (2014), 10.1103/PhysRevE.89.020301] present results from a molecular dynamics trajectory illustrating coarsening of ice, which they interpret as evidence of transient coexistence between two distinct supercooled phases of liquid water. We point out that neither two distinct liquids nor criticality are demonstrated in this simulation study. Instead, the illustrated trajectory is consistent with coarsening behaviors analyzed and predicted in earlier work by others.

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.

A general ionic liquid pH-zone-refining countercurrent chromatography method for separation of alkaloids from Nelumbo nucifera Gaertn.

PubMed

Fang, Yingtong; Li, Quan; Shao, Qian; Wang, Binghai; Wei, Yun

2017-07-21

The alkaloids from lotus (Nelumbo nucifera Gaertn) are effective in lowering hyperlipemia and level of cholesterol. However, there is not a general method for their separation. In this work, a general ionic liquid pH-zone-refining countercurrent chromatography method for isolation and purification of six alkaloids from the whole lotus plant was successfully established by using ionic liquids as the modifier of the two-phase solvent system. The conditions of ionic liquid pH-zone-refining countercurrent chromatography, involving solvent systems, concentration of retainer and eluter, types of ionic liquids, the content of ionic liquids as well as ionic liquids posttreatment, were optimized to improve extraction efficiency. Finally, the separation of these six alkaloids was performed with a two-phase solvent system composed of n-hexane-ethyl acetate-methanol-water-[C 4 mim][PF 6 ] at a volume ratio of 5:2:2:8:0.1, where 10mM TEA was added to the organic stationary phase as a retainer and 3mM HCl was added to the aqueous mobile phase as an eluter. As a result, six alkaloids including N-nornuciferine, liensinine, nuciferine, isoliensinine, roemerine and neferine were successfully separated with the purities of 97.0%, 90.2%, 94.7%, 92.8%, 90.4% and 95.9%, respectively. The established general method has been respectively applied to the crude samples of lotus leaves and lotus plumules. A total of 37.3mg of liensinine, 57.7mg of isoliensinine and 179.9mg of neferine were successfully purified in one run from 1.00g crude extract of lotus plumule with the purities of 93.2%, 96.5% and 98.8%, respectively. Amount of 45.6mg N-nornuciferine, 21.6mg nuciferine and 11.7mg roemerine was obtained in one step separation from 1.05g crude extract of lotus leaves with the purity of 96.9%, 95.6% and 91.33%, respectively. Copyright © 2017 Elsevier B.V. All rights reserved.

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.

Superbase-derived protic ionic liquid extractants for metal ion separation

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

Bell, Jason R.; Dai, Sheng; Luo, Huimin

2014-04-19

Solvent extraction of La 3+ and Ba 2+ by an ionic liquid extractant in an imidazolium-based ionic liquid diluent was investigated. Seven protic ionic liquid extractants were examined and these protic ILs are based on five organic superbases and either 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octadione (Hfod) or 1,1,1,5,5,5-hexafluoroacetylacetone (Hhfac) -diketones as anion. For fod-based extractants, the extraction efficiencies and separation factors were found to be concentration dependent. The effects of aqueous phase acidity, extractant structure, and extractant concentration on separation properties of La 3+ and Ba 2+ are discussed in this paper.

Integration of phase separation with ultrasound-assisted salt-induced liquid-liquid microextraction for analyzing the fluoroquinones in human body fluids by liquid chromatography.

PubMed

Wang, Huili; Gao, Ming; Wang, Mei; Zhang, Rongbo; Wang, Wenwei; Dahlgren, Randy A; Wang, Xuedong

2015-03-15

Herein, we developed a novel integrated device to perform phase separation based on ultrasound-assisted salt-induced liquid-liquid microextraction for determination of five fluoroquinones (FQs) in human body fluids. The integrated device consisted of three simple HDPE components used to separate the extraction solvent from the aqueous phase prior to retrieving the extractant. A series of extraction parameters were optimized using the response surface method based on central composite design. Optimal conditions consisted of 945μL acetone extraction solvent, pH 2.1, 4.1min stir time, 5.9g Na2SO4, and 4.0min centrifugation. Under optimized conditions, the limits of detection (at S/N=3) were 0.12-0.66μgL(-1), the linear range was 0.5-500μgL(-1) and recoveries were 92.6-110.9% for the five FQs extracted from plasma and urine. The proposed method has several advantages, such as easy construction from inexpensive materials, high extraction efficiency, short extraction time, and compatibility with HPLC analysis. Thus, this method shows excellent prospects for sample pretreatment and analysis of FQs in human body fluids. Copyright © 2015 Elsevier B.V. All rights reserved.

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.

Dehydrogenation of liquid fuel in microchannel catalytic reactor

DOEpatents

Toseland, Bernard Allen; Pez, Guido Peter; Puri, Pushpinder Singh

2010-08-03

The present invention is an improved process for the storage and delivery of hydrogen by the reversible hydrogenation/dehydrogenation of an organic compound wherein the organic compound is initially in its hydrogenated state. The improvement in the route to generating hydrogen is in the dehydrogenation step and recovery of the dehydrogenated organic compound resides in the following steps: introducing a hydrogenated organic compound to a microchannel reactor incorporating a dehydrogenation catalyst; effecting dehydrogenation of said hydrogenated organic compound under conditions whereby said hydrogenated organic compound is present as a liquid phase; generating a reaction product comprised of a liquid phase dehydrogenated organic compound and gaseous hydrogen; separating the liquid phase dehydrogenated organic compound from gaseous hydrogen; and, recovering the hydrogen and liquid phase dehydrogenated organic compound.

Dehydrogenation of liquid fuel in microchannel catalytic reactor

DOEpatents

Toseland, Bernard Allen [Allentown, PA; Pez, Guido Peter [Allentown, PA; Puri, Pushpinder Singh [Emmaus, PA

2009-02-03

The present invention is an improved process for the storage and delivery of hydrogen by the reversible hydrogenation/dehydrogenation of an organic compound wherein the organic compound is initially in its hydrogenated state. The improvement in the route to generating hydrogen is in the dehydrogenation step and recovery of the dehydrogenated organic compound resides in the following steps: introducing a hydrogenated organic compound to a microchannel reactor incorporating a dehydrogenation catalyst; effecting dehydrogenation of said hydrogenated organic compound under conditions whereby said hydrogenated organic compound is present as a liquid phase; generating a reaction product comprised of a liquid phase dehydrogenated organic compound and gaseous hydrogen; separating the liquid phase dehydrogenated organic compound from gaseous hydrogen; and, recovering the hydrogen and liquid phase dehydrogenated organic compound.

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%.

Unlocking the potential of supported liquid phase catalysts with supercritical fluids: low temperature continuous flow catalysis with integrated product separation

PubMed Central

Franciò, Giancarlo; Hintermair, Ulrich; Leitner, Walter

2015-01-01

Solution-phase catalysis using molecular transition metal complexes is an extremely powerful tool for chemical synthesis and a key technology for sustainable manufacturing. However, as the reaction complexity and thermal sensitivity of the catalytic system increase, engineering challenges associated with product separation and catalyst recovery can override the value of the product. This persistent downstream issue often renders industrial exploitation of homogeneous catalysis uneconomical despite impressive batch performance of the catalyst. In this regard, continuous-flow systems that allow steady-state homogeneous turnover in a stationary liquid phase while at the same time effecting integrated product separation at mild process temperatures represent a particularly attractive scenario. While continuous-flow processing is a standard procedure for large volume manufacturing, capitalizing on its potential in the realm of the molecular complexity of organic synthesis is still an emerging area that requires innovative solutions. Here we highlight some recent developments which have succeeded in realizing such systems by the combination of near- and supercritical fluids with homogeneous catalysts in supported liquid phases. The cases discussed exemplify how all three levels of continuous-flow homogeneous catalysis (catalyst system, separation strategy, process scheme) must be matched to locate viable process conditions. PMID:26574523

Unlocking the potential of supported liquid phase catalysts with supercritical fluids: low temperature continuous flow catalysis with integrated product separation.

PubMed

Franciò, Giancarlo; Hintermair, Ulrich; Leitner, Walter

2015-12-28

Solution-phase catalysis using molecular transition metal complexes is an extremely powerful tool for chemical synthesis and a key technology for sustainable manufacturing. However, as the reaction complexity and thermal sensitivity of the catalytic system increase, engineering challenges associated with product separation and catalyst recovery can override the value of the product. This persistent downstream issue often renders industrial exploitation of homogeneous catalysis uneconomical despite impressive batch performance of the catalyst. In this regard, continuous-flow systems that allow steady-state homogeneous turnover in a stationary liquid phase while at the same time effecting integrated product separation at mild process temperatures represent a particularly attractive scenario. While continuous-flow processing is a standard procedure for large volume manufacturing, capitalizing on its potential in the realm of the molecular complexity of organic synthesis is still an emerging area that requires innovative solutions. Here we highlight some recent developments which have succeeded in realizing such systems by the combination of near- and supercritical fluids with homogeneous catalysts in supported liquid phases. The cases discussed exemplify how all three levels of continuous-flow homogeneous catalysis (catalyst system, separation strategy, process scheme) must be matched to locate viable process conditions. © 2015 The Authors.

Stability of dense liquid carbon dioxide.

PubMed

Boates, Brian; Teweldeberhan, Amanuel M; Bonev, Stanimir A

2012-09-11

We present ab initio calculations of the phase diagram of liquid CO(2) and its melting curve over a wide range of pressure and temperature conditions, including those relevant to the Earth. Several distinct liquid phases are predicted up to 200 GPa and 10,000 K based on their structural and electronic characteristics. We provide evidence for a first-order liquid-liquid phase transition with a critical point near 48 GPa and 3,200 K that intersects the mantle geotherm; a liquid-liquid-solid triple point is predicted near 45 GPa and 1,850 K. Unlike known first-order transitions between thermodynamically stable liquids, the coexistence of molecular and polymeric CO(2) phases predicted here is not accompanied by metallization. The absence of an electrical anomaly would be unique among known liquid-liquid transitions. Furthermore, the previously suggested phase separation of CO(2) into its constituent elements at lower mantle conditions is examined by evaluating their Gibbs free energies. We find that liquid CO(2) does not decompose into carbon and oxygen up to at least 200 GPa and 10,000 K.

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 .

Comprehensive analysis of pharmaceutical products using simultaneous mixed-mode (ion-exchange/reversed-phase) and hydrophilic interaction liquid chromatography.

PubMed

Kazarian, Artaches A; Nesterenko, Pavel N; Soisungnoen, Phimpha; Burakham, Rodjana; Srijaranai, Supalax; Paull, Brett

2014-08-01

Liquid chromatographic assays were developed using a mixed-mode column coupled in sequence with a hydrophilic interaction liquid chromatography column to allow the simultaneous comprehensive analysis of inorganic/organic anions and cations, active pharmaceutical ingredients, and excipients (carbohydrates). The approach utilized dual sample injection and valve-mediated column switching and was based upon a single high-performance liquid chromatography gradient pump. The separation consisted of three distinct sequential separation mechanisms, namely, (i) ion-exchange, (ii) mixed-mode interactions under an applied dual gradient (reversed-phase/ion-exchange), and (iii) hydrophilic interaction chromatography. Upon first injection, the Scherzo SS C18 column (Imtakt) provided resolution of inorganic anions and cations under isocratic conditions, followed by a dual organic/salt gradient to elute active pharmaceutical ingredients and their respective organic counterions and potential degradants. At the top of the mixed-mode gradient (high acetonitrile content), the mobile phase flow was switched to a preconditioned hydrophilic interaction liquid chromatography column, and the standard/sample was reinjected for the separation of hydrophilic carbohydrates, some of which are commonly known excipients in drug formulations. The approach afforded reproducible separation and resolution of up to 23 chemically diverse solutes in a single run. The method was applied to investigate the composition of commercial cough syrups (Robitussin®), allowing resolution and determination of inorganic ions, active pharmaceutical ingredients, excipients, and numerous well-resolved unknown peaks. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Comparison of liquid and supercritical fluid chromatography mobile phases for enantioselective separations on polysaccharide stationary phases.

PubMed

Khater, Syame; Lozac'h, Marie-Anne; Adam, Isabelle; Francotte, Eric; West, Caroline

2016-10-07

Analysis and production of enantiomerically pure compounds is a major topic of interest when active pharmaceutical ingredients are concerned. Enantioselective chromatography has become a favourite both at the analytical and preparative scales. High-performance liquid chromatography (HPLC) and supercritical fluid chromatography (SFC) are dominating the scene and are often seen as complementary techniques. Nowadays, for economic and ecologic reasons, SFC may be preferred over normal-phase HPLC (NPLC) as it allows significant reductions in solvent consumption. However, the transfer of NPLC methods to SFC is not always straightforward. In this study, we compare the retention of achiral molecules and separation of enantiomers under supercritical fluid (carbon dioxide with ethanol or isopropanol) and liquid normal-phase (heptane with ethanol or isopropanol) elution modes with polysaccharide stationary phases in order to explore the differences between the retention and enantioseparation properties between the two modes. Chemometric methods (namely quantitative structure-retention relationships and discriminant analysis) are employed to compare the results obtained on a large set of analytes (171 achiral probes and 97 racemates) and gain some understanding on the retention and separation mechanisms. The results indicate that, contrary to popular belief, carbon dioxide - solvent SFC mobile phases are often weaker eluents than liquid mobile phases. It appears that SFC and NPLC elution modes provide different retention mechanisms. While some enantioseparations are unaffected, facilitating the transfer between the two elution modes, other enantioseparations may be drastically different due to different types and strength of interactions contributing to enantioselectivity. Copyright © 2016 Elsevier B.V. All rights reserved.

Surface-bonded ionic liquid stationary phases in high-performance liquid chromatography--a review.

PubMed

Pino, Verónica; Afonso, Ana M

2012-02-10

Ionic liquids (ILs) are a class of ionic, nonmolecular solvents which remain in liquid state at temperatures below 100°C. ILs possess a variety of properties including low to negligible vapor pressure, high thermal stability, miscibility with water or a variety of organic solvents, and variable viscosity. IL-modified silica as novel high-performance liquid chromatography (HPLC) stationary phases have attracted considerable attention for their differential behavior and low free-silanol activity. Indeed, around 21 surface-confined ionic liquids (SCIL) stationary phases have been developed in the last six years. Their chromatographic behavior has been studied, and, despite the presence of a positive charge on the stationary phase, they showed considerable promise for the separation of neutral solutes (not only basic analytes), when operated in reversed phase mode. This aspect points to the potential for truly multimodal stationary phases. This review attempts to summarize the state-of-the-art about SCIL phases including their preparation, chromatographic behavior, and analytical performance. Copyright © 2011 Elsevier B.V. All rights reserved.

Separation and purification of thymopentin with molecular imprinting membrane by solid phase extraction disks.

PubMed

Wang, Chaoli; Hu, Xiaoling; Guan, Ping; Wu, Danfeng; Qian, Liwei; Li, Ji; Song, Renyuan

2015-01-01

The synthesis and performance of molecularly imprinted membranes (MIMs) as a solid phase extraction packing materials for the separation and purification of thymopentin from crude samples was described. In order to increase structural selectivity and imprinting efficiency, surface-initiated ATRP and ionic liquid (1-vinyl-3-ethyl acetate imidazolium chloride) were used to prepare molecularly imprinting membranes. The results demonstrated that solid phase extraction disks stuffed by MIMs with ionic liquids as functional monomer demonstrated high isolation and purification of performance to the thymopentin. The molecular recognition of thymopentin was analyzed by using molecular modeling software. Copyright © 2014 Elsevier B.V. All rights reserved.

Liquid microjunction surface sampling coupled with high-pressure liquid chromatography-electrospray ionization-mass spectrometry for analysis of drugs and metabolites in whole-body thin tissue sections.

PubMed

Kertesz, Vilmos; Van Berkel, Gary J

2010-07-15

In this work, a commercially available autosampler was adapted to perform direct liquid microjunction (LMJ) surface sampling followed by a high-pressure liquid chromatography (HPLC) separation of the extract components and detection with electrospray ionization mass spectrometry (ESI-MS). To illustrate the utility of coupling a separation with this direct liquid extraction based surface sampling approach, four different organs (brain, lung, kidney, and liver) from whole-body thin tissue sections of propranolol dosed and control mice were examined. The parent drug was observed in the chromatograms of the surface sampling extracts from all the organs of the dosed mouse examined. In addition, two isomeric phase II metabolites of propranolol (an aliphatic and an aromatic hydroxypropranolol glucuronide) were observed in the chromatograms of the extracts from lung, kidney, and liver. Confirming the presence of one or the other or both of these glucuronides in the extract from the various organs was not possible without the separation. These drug and metabolite data obtained using the LMJ surface sampling/HPLC-MS method and the results achieved by analyzing similar samples by conventional extraction of the tissues and subsequent HPLC-MS analysis were consistent. The ability to directly and efficiently sample from thin tissue sections via a liquid extraction and then perform a subsequent liquid phase separation increases the utility of this liquid extraction surface sampling approach.

A Guided Inquiry Liquid/Liquid Extractions Laboratory for Introductory Organic Chemistry

ERIC Educational Resources Information Center

Raydo, Margaret L.; Church, Megan S.; Taylor, Zane W.; Taylor, Christopher E.; Danowitz, Amy M.

2015-01-01

A guided inquiry laboratory experiment for teaching liquid/liquid extractions to first semester undergraduate organic chemistry students is described. This laboratory is particularly useful for introductory students as the analytes that are separated are highly colored dye molecules. This allows students to track into which phase each analyte…

Charge Transport and Phase Behavior of Imidazolium-Based Ionic Liquid Crystals from Fully Atomistic Simulations

PubMed Central

2018-01-01

Ionic liquid crystals occupy an intriguing middle ground between room-temperature ionic liquids and mesostructured liquid crystals. Here, we examine a non-polarizable, fully atomistic model of the 1-alkyl-3-methylimidazolium nitrate family using molecular dynamics in the constant pressure–constant temperature ensemble. These materials exhibit a distinct “smectic” liquid phase, characterized by layers formed by the molecules, which separate the ionic and aliphatic moieties. In particular, we discuss the implications this layering may have for electrolyte applications. PMID:29301305

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.

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.

Reverse-mode thermoresponsive light attenuators produced by optical anisotropic composites of nematic liquid crystals and reactive mesogens

NASA Astrophysics Data System (ADS)

Kakiuchida, Hiroshi; Ogiwara, Akifumi

2018-04-01

Polymer network liquid crystals (PNLCs) whose optical transmittance state switches between transparence at low temperatures and haze at high temperatures were fabricated from mixtures of nematic liquid crystals (LCs) and reactive mesogens (RMs). This PNLC structure is simple but effective, namely, consists of micro-scale domains of orientation-ordered LCs and anisotropically polymerized RMs. The domains form through photopolymerization induced phase separation with inhomogeneous irradiation projected by laser speckling techniques. This irradiation method enables you to control the size and shape of phase-separation domains, and these PNLCs can be applied to novel thermoresponsive optical devices; optical isolators, thermometric sheets, and smart windows.

Evidence for phase separation of ethanol-water mixtures at the hydrogen terminated nanocrystalline diamond surface.

PubMed

Janssens, Stoffel D; Drijkoningen, Sien; Saitner, Marc; Boyen, Hans-Gerd; Wagner, Patrick; Larsson, Karin; Haenen, Ken

2012-07-28

Interactions between ethanol-water mixtures and a hydrophobic hydrogen terminated nanocrystalline diamond surface, are investigated by sessile drop contact angle measurements. The surface free energy of the hydrophobic surface, obtained with pure liquids, differs strongly from values obtained by ethanol-water mixtures. Here, a model which explains this difference is presented. The model suggests that, due to a higher affinity of ethanol for the hydrophobic surface, when compared to water, a phase separation occurs when a mixture of both liquids is in contact with the H-terminated diamond surface. These results are supported by a computational study giving insight in the affinity and related interaction at the liquid-solid interface.

Evaluation of ionic liquid stationary phases for one dimensional gas chromatography-mass spectrometry and comprehensive two dimensional gas chromatographic analyses of fatty acids in marine biota.

PubMed

Gu, Qun; David, Frank; Lynen, Frédéric; Vanormelingen, Pieter; Vyverman, Wim; Rumpel, Klaus; Xu, Guowang; Sandra, Pat

2011-05-20

Ionic liquid stationary phases were tested for one dimensional gas chromatography-mass spectrometry (GC-MS) and comprehensive two dimensional gas chromatography (GC×GC) of fatty acid methyl esters from algae. In comparison with polyethylene glycol and cyanopropyl substituted polar stationary phases, ionic liquid stationary phases SLB-IL 82 and SLB-IL 100 showed comparable resolution, but lower column bleeding with MS detection, resulting in better sensitivity. The selectivity and polarity of the ionic liquid phases are similar to a highly polar biscyanopropyl-silicone phase (e.g. HP-88). In GC×GC, using an apolar polydimethyl siloxane×polar ionic liquid column combination, an excellent group-type separation of fatty acids with different carbon numbers and number of unsaturations was obtained, providing information that is complementary to GC-MS identification. Copyright © 2011 Elsevier B.V. All rights reserved.

Deep eutectic liquid organic salt as a new solvent for liquid-phase microextraction and its application in ligandless extraction and preconcentraion of lead and cadmium in edible oils.

PubMed

Karimi, Mehdi; Dadfarnia, Shayessteh; Shabani, Ali Mohammad Haji; Tamaddon, Fatemeh; Azadi, Davood

2015-11-01

Deep eutectic liquid organic salt was used as the solvent and a liquid phase microextraction (DES-LPME) combined with electrothermal atomic absorption spectrometry (ETAAS) was developed for separation, preconcentration and determination of lead and cadmium in edible oils. A 4:1 mixture of deep eutectic solvent and 2% nitric acid (200 µL) was added to an oil sample. The mixture was vortexed and transferred into a water bath at 50 °C and stirred for 5 minutes. After the extraction was completed, the phases were separated by centrifugation, and the enriched analytes in the deep eutectic solvent phase were determined by ETAAS. Under optimized extraction conditions and for an oil sample of 28 g, enhancement factors of 198 and 195 and limits of detection (defined as 3 Sb/m) of 8 and 0. 2 ng kg(-1) were achieved for lead and cadmium respectively. The method was successfully applied to the determination of lead and cadmium in various edible oils. Copyright © 2015. Published by Elsevier B.V.

On the use of ionic liquids as mobile phase additives in high-performance liquid chromatography. A review.

PubMed

García-Alvarez-Coque, M C; Ruiz-Angel, M J; Berthod, A; Carda-Broch, S

2015-07-09

The popularity of ionic liquids (ILs) has grown during the last decades in several analytical separation techniques. Consequently, the number of reports devoted to the applications of ILs is still increasing. This review is focused on the use of ILs (mainly imidazolium-based associated to chloride and tetrafluoroborate) as mobile phase additives in high-performance liquid chromatography (HPLC). In this approach, ILs just function as salts, but keep several kinds of intermolecular interactions, which are useful for chromatographic separations. Both cation and anion can be adsorbed on the stationary phase, creating a bilayer. This gives rise to hydrophobic, electrostatic and other specific interactions with the stationary phase and solutes, which modify the retention behaviour and peak shape. This review updates the advances in this field, with emphasis on topics not always deeply considered in the literature, such as the mechanisms of retention, the estimation of the suppressing potency of silanols, modelling and optimisation of the chromatographic performance, and the comparison with other additives traditionally used to avoid the silanol problem. Copyright © 2015 Elsevier B.V. All rights reserved.

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

Hu, Michael Z.; Engtrakul, Chaiwat; Bischoff, Brian L.

A new class of inorganic-based membranes, i.e., High-Performance Architectured Surface Selective (HiPAS) membranes, is introduced to provide high perm-selective flux by exploiting unique separation mechanisms induced by superhydrophobic or superhydrophilic surface interactions and confined capillary condensation in enlarged membrane pores (~8 nm). The super-hydro-tunable HiPAS membranes were originally developed for the purpose of bio-oil/biofuel processing to achieve selective separations at higher flux relative to size selective porous membranes (e.g., inorganic zeolite-based membranes) and better high-temperature tolerance than polymer membranes (>250 C) for hot vapor processing. Due to surface-enhanced separation selectivity, HiPAS membranes can thus possibly enable larger pores to facilitatemore » large-flux separations by increasing from sub-nanometer pores to mesopores (2-50 nm) for vapor phase or micron-scale pores for liquid phase separations. In this paper, we describe an innovative membrane concept and a materials synthesis strategy to fabricate HiPAS membranes, and demonstrate selective permeation in both vapor- and liquid-phase applications. High permeability and selectivity were demonstrated using surrogate mixtures, such as ethanol-water, toluene-water, and toluene-phenol-water. The overall membrane evaluation results show promise for the future processing of biomass pyrolysis and upgraded product vapors and condensed liquid bio-oil intermediates.« less

[[Chiral separation of five arylpropionic acid drugs and determination of their enantiomers in pharmaceutical preparations by reversed-phase high performance liquid chromatography with cellulose-tris-(4-methylbenzoate) stationary phase

PubMed

Luo, An; Wan, Qiang; Fan, Huajun; Chen, Zhi; Wu, Xuehao; Huang, Xiaowen; Zang, Linquan

2014-09-01

Chromatographic behaviors for enantiomeric separation of arylpropionic acid drugs were systematically developed by reversed phase-high performance liquid chromatography (RP-HPLC) using cellulose-tris-(4-methylbenzoate) (CTMB) as chiral stationary phase (CSP). The effects of the composition of the mobile phase, additives and temperature on chiral separation of flurbiprofen, pranoprofen, naproxen, ibuprofen and loxoprofen were further investigated. The enantiomers had been successfully separated on CSP of CTMB by the mobile phase of methanol-0.1% (v/v) formic acid except naproxen by acetonitrile-0.1% (v/v) formic acid at 25 °C. The mechanisms of the racemic resolution for the above mentioned five drugs are discussed thermodynamically and structurally. The resolutions between respective enantiomers for arylpropionic acid drugs on CTMB had significant differences due to their chromatographic behaviors. The order of resolutions ranked pranoprofen, loxoprofen, flurbiprofen, ibuprofen and naproxen. The method established has been successfully applied to the determination of the enantiomers of the five drugs in commercial preparations under the optimized conditions. It proved that the method is simple, reliable and accurate.

SEPARATION OF VAPOR-PHASE ALCOHOL/WATER MIXTURES VIA FRACTIONAL CONDENSATION USING A PILOT-SCALE DEPHLEGMATOR: ENHANCEMENT OF THE PREVAPORATION PROCESS SEPARATION FACTOR

EPA Science Inventory

In prevaporation, a liquid mixture contacts a membrane surface that preferentially permeates one of the liquid components as a vapor. Our approach to improving pervaporation performance is to replace the one-stage condenser traditionally used to condense the permeate with a frac...

The physiological and pathological biophysics of phase separation and gelation of RNA binding proteins in amyotrophic lateral sclerosis and fronto-temporal lobar degeneration.

PubMed

St George-Hyslop, Peter; Lin, Julie Qiaojin; Miyashita, Akinori; Phillips, Emma C; Qamar, Seema; Randle, Suzanne J; Wang, GuoZhen

2018-04-30

Many RNA binding proteins, including FUS, contain moderately repetitive, low complexity, intrinsically disordered domains. These sequence motifs have recently been found to underpin reversible liquid: liquid phase separation and gelation of these proteins, permitting them to reversibly transition from a monodispersed state to liquid droplet- or hydrogel-like states. This function allows the proteins to serve as scaffolds for the formation of reversible membraneless intracellular organelles such as nucleoli, stress granules and neuronal transport granules. Using FUS as an example, this review examines the biophysics of this physiological process, and reports on how mutations and changes in post-translational state alter phase behaviour, and lead to neurodegenerative diseases such as amyotrophic lateral sclerosis and frontotemporal lobar degeneration. Copyright © 2018. Published by Elsevier B.V.

Self-interaction of NPM1 modulates multiple mechanisms of liquid-liquid phase separation.

PubMed

Mitrea, Diana M; Cika, Jaclyn A; Stanley, Christopher B; Nourse, Amanda; Onuchic, Paulo L; Banerjee, Priya R; Phillips, Aaron H; Park, Cheon-Gil; Deniz, Ashok A; Kriwacki, Richard W

2018-02-26

Nucleophosmin (NPM1) is an abundant, oligomeric protein in the granular component of the nucleolus with roles in ribosome biogenesis. Pentameric NPM1 undergoes liquid-liquid phase separation (LLPS) via heterotypic interactions with nucleolar components, including ribosomal RNA (rRNA) and proteins which display multivalent arginine-rich linear motifs (R-motifs), and is integral to the liquid-like nucleolar matrix. Here we show that NPM1 can also undergo LLPS via homotypic interactions between its polyampholytic intrinsically disordered regions, a mechanism that opposes LLPS via heterotypic interactions. Using a combination of biophysical techniques, including confocal microscopy, SAXS, analytical ultracentrifugation, and single-molecule fluorescence, we describe how conformational changes within NPM1 control valency and switching between the different LLPS mechanisms. We propose that this newly discovered interplay between multiple LLPS mechanisms may influence the direction of vectorial pre-ribosomal particle assembly within, and exit from the nucleolus as part of the ribosome biogenesis process.

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.

Separation and identification of neutral cereal lipids by normal phase high-performance liquid chromatography, using evaporative light-scattering and electrospray mass spectrometry for detection.

PubMed

Rocha, João M; Kalo, Paavo J; Ollilainen, Velimatti; Malcata, F Xavier

2010-04-30

A novel method was developed for the analysis of molecular species in neutral lipid classes, using separation by normal phase high-performance liquid chromatography, followed by detection by evaporative light-scattering and electrospray ionization tandem mass spectrometry. Monoacid standards, i.e. sterol esters, triacylglycerols, fatty acids, diacylglycerols, free sterols and monoacylglycerols, were separated to baseline on microbore 3 microm-silica gel columns. Complete or partial separation of molecular species in each lipid class permitted identification by automatic tandem mass spectrometry of ammonium adducts, produced via positive electrospray ionization. After optimization of the method, separation and identification of molecular species of various lipid classes was comprehensively tested by analysis of neutral lipids from the free lipid extract of maize flour. 2010 Elsevier B.V. All rights reserved.

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.

Wetting phenomenon in the liquid-vapor phase coexistence of a partially miscible Lennard-Jones binary mixture

NASA Astrophysics Data System (ADS)

Ramírez-Santiago, Guillermo; Díaz-Herrera, Enrique; Moreno Razo, José A.

2004-03-01

We have carried out extensive equilibrium MD simulations to study wetting phenomena in the liquid-vapor phase coexistence of a partially miscible binary LJ mixture. We find that in the temperature range 0.60 ≤ T^* < 0.80, the system separates forming a liquid A-liquid B interface in coexistence with the vapor phase. At higher temperatures, 0.80 ≤ T^* < 1.25 the liquid phases are wet by the vapor phase. By studying the behavior of the surface tension as a function of temperature we estimate the wetting transition temperature (WTT) to be T^*_w≃ 0.80. The adsorption of molecules at the liquid-liquid interface shows a discontinuity at about T^*≃ 0.79 suggesting that the wetting transition is a first order phase transition. These results are in agreement with some experiments carried out in fluid binary mixtures. In addition, we estimated the consolute temperature to be T^* _cons≃ 1.25. The calculated phase diagram of the mixture suggest the existence of a tricritical point.

Determination of volatile compounds in cider apple juices using a covalently bonded ionic liquid coating as the stationary phase in gas chromatography.

PubMed

Pello-Palma, Jairo; González-Álvarez, Jaime; Gutiérrez-Álvarez, María Dolores; Dapena de la Fuente, Enrique; Mangas-Alonso, Juan José; Méndez-Sánchez, Daniel; Gotor-Fernández, Vicente; Arias-Abrodo, Pilar

2017-04-01

A chromatographic method for the separation of volatile compounds in Asturian cider apple juices has been developed. For this separation purpose, a monocationic imidazolium-based ionic liquid bearing a reactive terminal iodine atom was synthesized by a quaternization-anion exchange chemical sequence. Next, the gas chromatography (GC) stationary phase was prepared by covalently linking the imidazolium monolith to the reactive silanol groups of the inner capillary wall at 70 °C. This coated GC column exhibited good thermal stability (290 °C), as well as good efficiency (2000 plates/m) in the separation of volatile compounds from Asturian apple cider juices, and was characterized using the Abraham solvation parameter model. The intra-day and inter-day precision of the chromatographic method was evaluated, obtaining relative standard deviations from 3.7 to 12.9% and from 7.4 to 18.0%, respectively. Furthermore, recoveries from 82.5 to 122% were achieved. Graphical Abstract Covalent bonding of an ionic liquid to inner column wall led to a great improvement of the separation efficiencies of stationary phases in gas chromatography.

Superhydrophobic and superhydrophilic surface-enhanced separation performance of porous inorganic membranes for biomass-to-biofuel conversion applications

DOE PAGES

Hu, Michael Z.; Engtrakul, Chaiwat; Bischoff, Brian L.; ...

2016-11-14

A new class of inorganic-based membranes, i.e., High-Performance Architectured Surface Selective (HiPAS) membranes, is introduced to provide high perm-selective flux by exploiting unique separation mechanisms induced by superhydrophobic or superhydrophilic surface interactions and confined capillary condensation in enlarged membrane pores (~8 nm). The super-hydro-tunable HiPAS membranes were originally developed for the purpose of bio-oil/biofuel processing to achieve selective separations at higher flux relative to size selective porous membranes (e.g., inorganic zeolite-based membranes) and better high-temperature tolerance than polymer membranes (>250 C) for hot vapor processing. Due to surface-enhanced separation selectivity, HiPAS membranes can thus possibly enable larger pores to facilitatemore » large-flux separations by increasing from sub-nanometer pores to mesopores (2-50 nm) for vapor phase or micron-scale pores for liquid phase separations. In this paper, we describe an innovative membrane concept and a materials synthesis strategy to fabricate HiPAS membranes, and demonstrate selective permeation in both vapor- and liquid-phase applications. High permeability and selectivity were demonstrated using surrogate mixtures, such as ethanol-water, toluene-water, and toluene-phenol-water. The overall membrane evaluation results show promise for the future processing of biomass pyrolysis and upgraded product vapors and condensed liquid bio-oil intermediates.« less

Facile preparation of an alternating copolymer-based high molecular shape-selective organic phase for reversed-phase liquid chromatography.

PubMed

Mallik, Abul K; Noguchi, Hiroki; Rahman, Mohammed Mizanur; Takafuji, Makoto; Ihara, Hirotaka

2018-06-22

The synthesis of a new alternating copolymer-grafted silica phase is described for the separation of shape-constrained isomers of polycyclic aromatic hydrocarbons (PAHs) and tocopherols in reversed-phase high-performance liquid chromatography (RP-HPLC). Telomerization of the monomers (octadecyl acrylate and N-methylmaleimide) was carried out with a silane coupling agent; 3-mercaptopropyltrimethoxysilane (MPS), and the telomer (T) was grafted onto porous silica surface to prepare the alternating copolymer-grafted silica phase (Sil-alt-T). The new hybrid material was characterized by elemental analyses, diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy, and solid-state 13 C and 29 Si cross-polarization magic-angle spinning (CP/MAS) NMR spectroscopy. The results of 13 C CP/MAS NMR demonstrated that the alkyl chains of the grafted polymers in Sil-alt-T remained disordered, amorphous, and mobile represented by gauche conformational form. Separation abilities and molecular-shape selectivities of the prepared organic phase were evaluated by the separation of PAHs isomers and Standard Reference Material 869b, Column Selectivity Test Mixture for Liquid Chromatography, respectively and compared with commercially available octadecylsilylated silica (ODS) and C 30 columns as well as previously reported alternating copolymer-based column. The effectiveness of this phase is also demonstrated by the separation of tocopherol isomers. Oriented functional groups along the polymer main chains and cavity formations are investigated to be the driving force for better separation with multiple-interactions with the solutes. One of the advantages of the Sil-alt-T phase to that of the previously reported phase is the synthesis of the telomer first and then immobilized onto silica surface. In this case, the telomer was characterized easily with simple spectroscopic techniques and the molecular mass and polydispersity index of the telomer were determined by size exclusion chromatography (SEC) before grafting onto silica surface. Moreover, both of the monomers were commercially available. Therefore, the technique of preparation was very facile and better separation was achieved with the Sil-alt-T phase compared to the ODS, C 30 and other previously reported alternating copolymer-based columns. Copyright © 2018 Elsevier B.V. All rights reserved.

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.

DNA - peptide polyelectrolyte complexes: Phase control by hybridization

NASA Astrophysics Data System (ADS)

Vieregg, Jeffrey; Lueckheide, Michael; Marciel, Amanda; Leon, Lorraine; Tirrell, Matthew

DNA is one of the most highly-charged molecules known, and interacts strongly with charged molecules in the cell. Condensation of long double-stranded DNA is one of the classic problems of biophysics, but the polyelectrolyte behavior of short and/or single-stranded nucleic acids has attracted far less study despite its importance for both biological and engineered systems. We report here studies of DNA oligonucleotides complexed with cationic peptides and polyamines. As seen previously for longer sequences, double-stranded oligonucleotides form solid precipitates, but single-stranded oligonucleotides instead undergo liquid-liquid phase separation to form coacervate droplets. Complexed oligonucleotides remain competent for hybridization, and display sequence-dependent environmental response. We observe similar behavior for RNA oligonucleotides, and methylphosphonate substitution of the DNA backbone indicates that nucleic acid charge density controls whether liquid or solid complexes are formed. Liquid-liquid phase separations of this type have been implicated in formation of membraneless organelles in vivo, and have been suggested as protocells in early life scenarios; oligonucleotides offer an excellent method to probe the physics controlling these phenomena.

Methods of calculating engineering parameters for gas separations

NASA Technical Reports Server (NTRS)

Lawson, D. D.

1980-01-01

A group additivity method has been generated which makes it possible to estimate, from the structural formulas alone, the energy of vaporization and the molar volume at 25 C of many nonpolar organic liquids. From these two parameters and appropriate thermodynamic relationships it is then possible to predict the vapor pressure of the liquid phase and the solubility of various gases in nonpolar organic liquids. The data are then used to evaluate organic and some inorganic liquids for use in gas separation stages or as heat exchange fluids in prospective thermochemical cycles for hydrogen production.

A hybrid liquid-phase precipitation (LPP) process in conjunction with membrane distillation (MD) for the treatment of the INEEL sodium-bearing liquid waste.

PubMed

Bader, M S H

2005-05-20

A novel hybrid system combining liquid-phase precipitation (LPP) and membrane distillation (MD) is integrated for the treatment of the INEEL sodium-bearing liquid waste. The integrated system provides a "full separation" approach that consists of three main processing stages. The first stage is focused on the separation and recovery of nitric acid from the bulk of the waste stream using vacuum membrane distillation (VMD). In the second stage, polyvalent cations (mainly TRU elements and their fission products except cesium along with aluminum and other toxic metals) are separated from the bulk of monovalent anions and cations (dominantly sodium nitrate) by a front-end LPP. In the third stage, MD is used first to concentrate sodium nitrate to near saturation followed by a rear-end LPP to precipitate and separate sodium nitrate along with the remaining minor species from the bulk of the aqueous phase. The LPP-MD hybrid system uses a small amount of an additive and energy to carry out the treatment, addresses multiple critical species, extracts an economic value from some of waste species, generates minimal waste with suitable disposal paths, and offers rapid deployment. As such, the LPP-MD could be a valuable tool for multiple needs across the DOE complex where no effective or economic alternatives are available.

Evaluation of effects of pH and ionic strength on colloidal stability of IgG solutions by PEG-induced liquid-liquid phase separation.

PubMed

Thompson, Ronald W; Latypov, Ramil F; Wang, Ying; Lomakin, Aleksey; Meyer, Julie A; Vunnum, Suresh; Benedek, George B

2016-11-14

Colloidal stability of IgG antibody solutions is important for pharmaceutical and medicinal applications. Solution pH and ionic strength are two key factors that affect the colloidal stability of protein solutions. In this work, we use a method based on the PEG-induced liquid-liquid phase separation to examine the effects of pH and ionic strength on the colloidal stability of IgG solutions. We found that at high ionic strength (≥0.25M), the colloidal stability of most of our IgGs is insensitive to pH, and at low ionic strength (≤0.15M), all IgG solutions are much more stable at pH 5 than at pH 7. In addition, the PEG-induced depletion force is less efficient in causing phase separation at pH 5 than at pH 7. In contrast to the native inter-protein interaction of IgGs, the effect of depletion force on phase separation of the antibody solutions is insensitive to ionic strength. Our results suggest that the long-range electrostatic inter-protein repulsion at low ionic strength stabilizes the IgG solutions at low pH. At high ionic strength, the short-range electrostatic interactions do not make a significant contribution to the colloidal stability for most IgGs with a few exceptions. The weaker effect of depletion force at lower pH indicates a reduction of protein concentration in the condensed phase. This work advances our basic understanding of the colloidal stability of IgG solutions and also introduces a practical approach to measuring protein colloidal stability under various solution conditions.

Enantioselective separation of racemic juvenile hormone III by normal-phase high-performance liquid chromatography and preparation of [(2)H(3)]juvenile hormone III as an internal standard for liquid chromatography-mass spectrometry quantification.

PubMed

Ichikawa, Akio; Ono, Hiroshi; Furuta, Kenjiro; Shiotsuki, Takahiro; Shinoda, Tetsuro

2007-08-17

Juvenile hormone III (JH III) racemate was prepared from methyl (2E,6E)-farnesoate via epoxidation with 3-chloroperbenzoic acid (mCPBA). Enantioselective separation of JH III was conducted using normal-phase high-performance liquid chromatography (HPLC) on a chiral stationary phase. [(2)H(3)]Methyl (2E,6E)-farnesoate was also prepared from (2E,6E)-farnesoic acid and [(2)H(4)]methanol (methanol-d(4)) using 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC) and 4-dimethylaminopyridine (DMAP); the conjugated double bond underwent isomerization to some degree. Epoxidation of [(2)H(3)]methyl (2E,6E)-farnesoate with mCPBA gave a novel deuterium-substituted internal standard [(2)H(3)]JH III (JH III-d(3)). The standard curve was produced by linear regression using the peak area ratios of JH III and JH III-d(3) in liquid chromatography-mass spectrometry (LC-MS).

Integrated acoustic phase separator and multiphase fluid composition monitoring apparatus and method

DOEpatents

Sinha, Dipen N.

2016-01-12

An apparatus and method for down hole gas separation from the multiphase fluid flowing in a wellbore or a pipe, for determining the quantities of the individual components of the liquid and the flow rate of the liquid, and for remixing the component parts of the fluid after which the gas volume may be measured, without affecting the flow stream, are described. Acoustic radiation force is employed to separate gas from the liquid, thereby permitting measurements to be separately made for these two components; the liquid (oil/water) composition is determined from ultrasonic resonances; and the gas volume is determined from capacitance measurements. Since the fluid flows around and through the component parts of the apparatus, there is little pressure difference, and no protection is required from high pressure differentials.

Integrated acoustic phase separator and multiphase fluid composition monitoring apparatus and method

DOEpatents

Sinha, Dipen N

2014-02-04

An apparatus and method for down hole gas separation from the multiphase fluid flowing in a wellbore or a pipe, for determining the quantities of the individual components of the liquid and the flow rate of the liquid, and for remixing the component parts of the fluid after which the gas volume may be measured, without affecting the flow stream, are described. Acoustic radiation force is employed to separate gas from the liquid, thereby permitting measurements to be separately made for these two components; the liquid (oil/water) composition is determined from ultrasonic resonances; and the gas volume is determined from capacitance measurements. Since the fluid flows around and through the component parts of the apparatus, there is little pressure difference, and no protection is required from high pressure differentials.

Simultaneous separation by reversed-phase high-performance liquid chromatography and mass spectral identification of anthocyanins and flavonols in Shiraz grape skin.

PubMed

Downey, Mark O; Rochfort, Simone

2008-08-01

A limitation of large-scale viticultural trials is the time and cost of comprehensive compositional analysis of the fruit by high-performance liquid chromatography (HPLC). In addition, separate methods have generally been required to identify and quantify different classes of metabolites. To address these shortcomings a reversed-phase HPLC method was developed to simultaneously separate the anthocyanins and flavonols present in grape skins. The method employs a methanol and water gradient acidified with 10% formic acid with a run-time of 48 min including re-equilibration. Identity of anthocyanins and flavonols in Shiraz (Vitis vinifera L.) skin was confirmed by mass spectral analysis.

Gradient separation of oligosaccharides and suppressing anomeric mutarotation with enhanced-fluidity liquid hydrophilic interaction chromatography.

PubMed

Bennett, Raffeal; Olesik, Susan V

2017-04-01

Enhanced fluidity liquid chromatography using the hydrophilic interaction retention mechanism (EFLC-HILIC) is studied as an alternative separation mode for analyzing oligosaccharides and other sugars. These carbohydrates, which are important for the study of foods and biological systems, are difficult to comprehensively profile and either require a non-green, expensive solvent (i.e. acetonitrile) or derivatization of the analytes at the expense of time, sample loss, and loss of quantitative information. These difficulties arise from the diverse isomerism, mutarotation, and lack of a useable chromophore/fluorophore for spectroscopic detection. Enhanced fluidity liquid chromatography is an alternative separation method that involves the use of conventional polar solvents, such as methanol/water mixtures, as the primary mobile phase component and liquid carbon dioxide (CO 2 ) as the modifier in subcritical conditions. The addition of liquid CO 2 enhances diffusivity and decreases viscosity while maintaining mixture polarity, which typically results in reduced time of analysis and higher efficiency. This work illustrates an optimized EFLC-HILIC separation of a test mixture of oligosaccharides and simple sugars with a resolution greater than 1.3 and an analysis time decrease of over 35% compared to a conventional HPLC HILIC-mode analysis using acetonitrile/water mobile phases. Copyright © 2017 Elsevier B.V. All rights reserved.

Development and validation of a liquid chromatography-tandem mass spectrometry method for the separation of conjugated and unconjugated 17alpha- and 17beta-boldenone in urine sample.

PubMed

Gasparini, Mara; Assini, Walter; Bozzoni, Eros; Tognoli, Nadia; Dusi, Guglielmo

2007-03-14

Natural occurrence or illegal treatment of boldenone (BOLD) presence in cattle urine is under debate within the European Union. Separation of conjugated and unconjugated forms of 17alpha-boldenone (alpha-BOLD) and 17beta-boldenone (beta-BOLD) and presence of related molecules as androsta-1,4-diene-3,17-dione (ADD) appear critical points for the decision of an illegal use. The aim of this study is a new analytical approach of BOLD and ADD confirmation in cattle urine. The separation between conjugated and unconjugated forms of BOLD was obtained by a preliminary urine liquid-liquid extraction step with ethyl acetate. In this step the organic phase extracts only unconjugated BOLD and ADD, while BOLD in conjugated form remain in urine phase. Afterwards the urine phase, contains conjugated BOLD, was subjected to an enzymatic deconjugation. Solid-phase extraction (OASIS-HLB Waters) was used for the purification and concentration of analytes in organic and urine phases and liquid chromatography ion electrospray tandem mass spectrometry (LC-MS-MS) was applied for the confirmation of BOLD and ADD, using deuterium-labelled 17beta-boldenone (BOLD-d3) as internal standard. The method was validated as a quantitative confirmatory method according to the Commission Decision 2002/657/CE. The results obtained demonstrate that the developed method show very high specificity, precision, trueness and ruggedness. Decision limits (CCalpha) smaller than 0.5 ng mL(-1) were obtained for each analyte.

Lower critical solution temperature (LCST) phase separation of glycol ethers for forward osmotic control.

PubMed

Nakayama, Daichi; Mok, Yeongbong; Noh, Minwoo; Park, Jeongseon; Kang, Sunyoung; Lee, Yan

2014-03-21

Lower critical solution temperature (LCST) phase transition of glycol ether (GE)-water mixtures induces an abrupt change in osmotic pressure driven by a mild temperature change. The temperature-controlled osmotic change was applied for the forward osmosis (FO) desalination. Among three GEs evaluated, di(ethylene glycol) n-hexyl ether (DEH) was selected as a potential FO draw solute. A DEH-water mixture with a high osmotic pressure could draw fresh water from a high-salt feed solution such as seawater through a semipermeable membrane at around 10 °C. The water-drawn DEH-water mixture was phase-separated into a water-rich phase and a DEH-rich phase at around 30 °C. The water-rich phase with a much reduced osmotic pressure released water into a low-salt solution, and the DEH-rich phase was recovered into the initial DEH-water mixture. The phase separation behaviour, the residual GE concentration in the water-rich phase, the osmotic pressure of the DEH-water mixture, and the osmotic flux between the DEH-water mixture and salt solutions were carefully analysed for FO desalination. The liquid-liquid phase separation of the GE-water mixture driven by the mild temperature change between 10 °C and 30 °C is very attractive for the development of an ideal draw solute for future practical FO desalination.

In Situ Activation of Microcapsules

NASA Technical Reports Server (NTRS)

Morrison, Dennis R. (Inventor); Mosier, Benjamin (Inventor)

2000-01-01

Disclosed are microcapsules comprising a polymer shell enclosing two or more immiscible liquid phases in which a drug, or a prodrug and a drug activator are partitioned into separate phases. or prevented from diffusing out of the microcapsule by a liquid phase in which the drug is poorly soluble. Also disclosed are methods of using the microcapsules for in situ activation of drugs where upon exposure to an appropriate energy source the internal phases mix and the drug is activated in situ.

Preparation and evaluation of surface-bonded tricationic ionic liquid silica as stationary phases for high-performance liquid chromatography.

PubMed

Qiao, Lizhen; Shi, Xianzhe; Lu, Xin; Xu, Guowang

2015-05-29

Two tricationic ionic liquids were prepared and then bonded onto the surface of supporting silica materials through "thiol-ene" click chemistry as new stationary phases for high-performance liquid chromatography. The obtained columns of tricationic ionic liquids were evaluated respectively in the reversed-phase liquid chromatography (RPLC) mode and hydrophilic interaction liquid chromatography (HILIC) mode, and possess ideal column efficiency of 80,000 plates/m in the RPLC mode with naphthalene as the test solute. The tricationic ionic liquid stationary phases exhibit good hydrophobic and shape selectivity to hydrophobic compounds, and RPLC retention behavior with multiple interactions. In the HILIC mode, the retention and selectivity were evaluated through the efficient separation of nucleosides and bases as well as flavonoids, and the typical HILIC retention behavior was demonstrated by investigating retention changes of hydrophilic solutes with water volume fraction in mobile phase. The results show that the tricationic ionic liquid columns possess great prospect for applications in analysis of hydrophobic and hydrophilic samples. 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.

Separation and quantitation of colour pigments of chili powder (Capsicum frutescens) by high-performance liquid chromatography-diode array detection.

PubMed

Cserháti, T; Forgács, E; Morais, M H; Mota, T; Ramos, A

2000-10-27

The performance of reversed-phase thin-layer (RP-TLC) and reversed-phase high-performance liquid chromatography (RP-HPLC) was compared for the separation and determination of the colour pigments of chili (Capsicum frutescens) powder using a wide variety of eluent systems. No separation of pigments was achieved in RP-TLC, however, it was established that tetrahydrofuran shows an unusually high solvent strength. RP-HPLC using water-methanol-acetonitrile gradient elution separated the chili pigments in many fractions. Diode array detection (DAD) indicated that yellow pigments are eluted earlier than the red ones and chili powder contains more yellow pigments than common paprika powders. It was established that the very different absorption spectra of pigments make the use of DAD necessary.

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

Containerless, Low-Gravity Undercooling of Ti-Ce Alloys in the MSFC Drop Tube

NASA Technical Reports Server (NTRS)

Robinson, M. B.; Rathz, T. J.; Li, D.; Williams, G.; Workman, G.

1999-01-01

Previous tests of the classical nucleation theory as applied to liquid-liquid gap miscibility systems found a discrepancy between experiment and theory in the ability to undercool one of the liquids before the L1-L2 separation occurs. To model the initial separation process in a two-phase liquid mixture, different theoretical approaches, such as free-energy gradient and density gradient theories, have been put forth. If there is a large enough interaction between the critical liquid and the crucible, both models predict a wetting temperature (T(sub w)) above which the minority liquid perfectly wets and layers the crucible interface, but only on one side of the immiscibility dome. Materials with compositions on the other side of the dome will have simple surface adsorption by the minority liquid before bulk separation occurs when the coexistence (i.e., binoidal) line in reached. If the interaction between the critical liquid and the crucible were to decrease, T(sub w) would increase, eventually approaching the critical consolute temperature (T(sub cc)). If this situation occurs, then there could be large regions of the miscibility gap where non-perfect wetting conditions prevail resulting in droplets of L1 liquid at the surface having a non-zero contact angle. The resulting bulk structure will then depend on what happens on the surface and the subsequent processing conditions. In the past several decades, many experiments in space have been performed on liquid metal binary immiscible systems for the purpose of determining the effects that different crucibles may have on the wetting and separation process of the liquids. Potard performed experiments that showed different crucible materials could cause the majority phase to preferentially wet the container and thus produce a dispersed microstructure of the minority phase. Several other studies have been performed on immiscibles in a semi-container environment using an emulsion technique. Only one previous study was performed using completely containerless processing of immiscible metals and the results of that investigation are similar to some of the emulsion studies. In all the studies, surface wetting was attributed as the cause for the similar microstructures or the asymmetry in the ability to undercool the liquid below the binoidal on one side of the immiscibility dome. By removing the container completely from the separation process, it was proposed that the loss of the crucible/liquid interaction would produce a large shift in T(sub w) and thus change the wetting characteristics at the surface. By investigating various compositions across the miscibility gap, a change in the type and amount of liquid wetting at the surface of a containerless droplet should change the surface nucleating behavior of the droplet - whether it be the liquid-liquid wetting or the liquid-to-solid transition. Undercooling of the liquid into the metastable region should produce significant differences in the separation process and the microstructure upon solidification. In this study, we attempt to measure these transitions by monitoring the temperature of the sample by optical pyrometry. Microstructural analysis will be made to correlate with the degree of undercooling and the separation mechanisms involved.

Nano-liquid chromatography applied to enantiomers separation.

PubMed

Fanali, Salvatore

2017-02-24

This paper presents the state of the art concerning the separation of chiral compounds by means of nano-liquid chromatography (nano-LC). The enantiomers' separation and determination are a subject of fundamental importance in various application fields such as pharmaceutical industry, biomedicine, food, agrochemical etc. Nano-LC is a miniaturized chromatographic technique offering some advantages over conventional ones such as low consumption of mobile phase, sample volume and amount of chiral stationary phase, reduced costs etc. This is reported in the first part of the paper illustrating the features of the nano-LC. In addition, chiral resolution methods are briefly illustrated. Some chiral selectors, used in high-performance liquid chromatography have also been applied in nano-LC including cyclodextrins, glycopeptide antibiotics, modified polysaccharides etc. This is discussed in the second part of the review. Finally some examples of the applications available in literature are reported. Copyright © 2016 Elsevier B.V. All rights reserved.

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.

Binary Colloidal Alloy Test-3 and 4: Critical Point

NASA Technical Reports Server (NTRS)

Weitz, David A.; Lu, Peter J.

2007-01-01

Binary Colloidal Alloy Test - 3 and 4: Critical Point (BCAT-3-4-CP) will determine phase separation rates and add needed points to the phase diagram of a model critical fluid system. Crewmembers photograph samples of polymer and colloidal particles (tiny nanoscale spheres suspended in liquid) that model liquid/gas phase changes. Results will help scientists develop fundamental physics concepts previously cloaked by the effects 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.

Separation of cannabinoids on three different mixed-mode columns containing carbon/nanodiamond/amine-polymer superficially porous particles.

PubMed

Hung, Chuan-Hsi; Zukowski, Janusz; Jensen, David S; Miles, Andrew J; Sulak, Clayton; Dadson, Andrew E; Linford, Matthew R

2015-09-01

Three mixed-mode high-performance liquid chromatography columns packed with superficially porous carbon/nanodiamond/amine-polymer particles were used to separate mixtures of cannabinoids. Columns evaluated included: (i) reversed phase (C18 ), weak anion exchange, 4.6 × 33 mm, 3.6 μm, and 4.6 × 100 mm, 3.6 μm, (ii) reversed phase, strong anion exchange (quaternary amine), 4.6×33 mm, 3.6 μm, and (iii) hydrophilic interaction liquid chromatography, 4.6 × 150 mm, 3.6 μm. Different selectivities were achieved under various mobile phase and stationary phase conditions. Efficiencies and peak capacities were as high as 54 000 N/m and 56, respectively. The reversed phase mixed-mode column (C18 ) retained tetrahydrocannabinolic acid strongly under acidic conditions and weakly under basic conditions. Tetrahydrocannabinolic acid was retained strongly on the reversed phase, strong anion exchange mixed-mode column under basic polar organic mobile phase conditions. The hydrophilic interaction liquid chromatography column retained polar cannabinoids better than the (more) neutral ones under basic conditions. A longer reversed phase (C18 ) mixed-mode column (4.6 × 100 mm) showed better resolution for analytes (and a contaminant) than a shorter column. Fast separations were achieved in less than 5 min and sometimes 2 min. A real world sample (bubble hash extract) was also analyzed by gradient elution. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Separation and concentration of lower alcohols from dilute aqueous solutions

DOEpatents

Moore, Raymond H.; Eakin, David E.; Baker, Eddie G.; Hallen, Richard T.

1991-01-01

A process for producing, from a dilute aqueous solution of a lower (C.sub.1 -C.sub.5) alcohol, a concentrated liquid solution of the alcohol in an aromatic organic solvent is disclosed. Most of the water is removed from the dilute aqueous solution of alcohol by chilling sufficiently to form ice crystals. Simultaneously, the remaining liquid is extracted at substantially the same low temperature with a liquid organic solvent that is substantially immiscible in aqueous liquids and has an affinity for the alcohol at that temperature, causing the alcohol to transfer to the organic phase. After separating the organic liquid from the ice crystals, the organic liquid can be distilled to enrich the concentration of alcohol therein. Ethanol so separated from water and concentrated in an organic solvent such as toluene is useful as an anti-knock additive for gasoline.

Highly hydrophilic and nonionic poly(2-vinyloxazoline)-grafted silica: a novel organic phase for high-selectivity hydrophilic interaction chromatography.

PubMed

Mallik, Abul K; Cheah, Wee Keat; Shingo, Kaori; Ejzaki, Aika; Takafuji, Makoto; Ihara, Hirotaka

2014-07-01

A new hydrophilic and nonionic poly(2-vinyloxazoline)-grafted silica (Sil-VOX(n)) phase was synthesized and applied for the separation of nucleosides and nucleobases in hydrophilic interaction chromatography (HILIC). Polymerization and immobilization onto silica were confirmed by using characterization techniques including (1)H NMR spectroscopy, elemental analysis, and diffuse reflectance infrared Fourier transform spectroscopy. The hydrophilicity or wettability of Sil-VOX(n) was observed by measuring the contact angle (59.9°). The chromatographic results were compared with those obtained with a conventional HILIC silica column. The Sil-VOX(n) phase showed much better separation of polar test analytes than the silica column, and the elution order was different. Differences in selectivity between these two columns indicate that the stationary phase cannot function merely as an inert support for a water layer into which the solutes are partitioned from the bulk mobile phase. To elucidate the interaction mechanism, the separation of dihydroxybenzene isomers was performed on both columns in normal-phase liquid chromatography. Sil-VOX(n) was very sensitive to the dipole moments of the positional isomers of polycyclic aromatic compounds in normal-phase liquid chromatography. The interaction mechanism for Sil-VOX(n) in HILIC separation is also described.

Automated hollow-fiber liquid-phase microextraction followed by liquid chromatography with mass spectrometry for the determination of benzodiazepine drugs in biological samples.

PubMed

Nazaripour, Ali; Yamini, Yadollah; Ebrahimpour, Behnam; Fasihi, Javad

2016-07-01

In this study, two-phase hollow-fiber liquid-phase microextraction and three-phase hollow-fiber liquid-phase microextraction based on two immiscible organic solvents were compared for extraction of oxazepam and Lorazepam. Separations were performed on a liquid chromatography with mass spectrometry instrument. Under optimal conditions, three-phase hollow-fiber liquid-phase microextraction based on two immiscible organic solvents has a better extraction efficiency. In a urine sample, for three-phase hollow fiber liquid-phase microextraction based on two immiscible organic solvents, the calibration curves were found to be linear in the range of 0.6-200 and 0.9-200 μg L(-1) and the limits of detection were 0.2 and 0.3 μg L(-1) for oxazepam and lorazepam, respectively. For two-phase hollow fiber liquid-phase microextraction, the calibration curves were found to be linear in the range of 1-200 and 1.5-200 μg L(-1) and the limits of detection were 0.3 and 0.5 μg L(-1) for oxazepam and lorazepam, respectively. In a urine sample, for three-phase hollow-fiber-based liquid-phase microextraction based on two immiscible organic solvents, relative standard deviations in the range of 4.2-4.5% and preconcentration factors in the range of 70-180 were obtained for oxazepam and lorazepam, respectively. Also for the two-phase hollow-fiber liquid-phase microextraction, preconcentration factors in the range of 101-257 were obtained for oxazepam and lorazepam, respectively. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Liquid chromatographic separation of terpenoid pigments in foods and food products.

PubMed

Cserháti, T; Forgács, E

2001-11-30

The newest achievements in the use of various liquid chromatographic techniques such as adsorption and reversed-phase thin-layer chromatography and HPLC employed for the separation and quantitative determination of terpenoid-based color substances in foods and food products are reviewed. The techniques applied for the analysis of individual pigments and pigments classes are surveyed and critically evaluated. Future trends in the separation and identification of pigments in foods and food products are delineated.

Size exclusion chromatographic analysis of refuse-derived fuel for mycotoxins

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

Bicking, M.K.; Kniseley, R.N.

1980-11-01

A Styragel packing material is characterized in several solvent systems by using a series of test solutes and mycotoxins. Differences in interpretation with other work are discussed. Three different separation modes are generated on one stationary phase. An improved separation of mycotoxins from a compilcated matrix results by simultaneously using size exclusion and liquid-liquid partitioning. 4 figures, 3 tables.

Solid-phase extraction and high-performance liquid chromatographic separation of pigments of red wines.

PubMed

Csiktusnádi Kiss, G A; Forgács, E; Cserháti, T; Candeias, M; Vilas-Boas, L; Bronze, R; Spranger, I

2000-08-11

The adsorption and desorption capacities of 11 different solid-phase extraction sorbents were tested for the preconcenration of pigments of various Hungarian red wines. The concentrates were evaluated by multiwavelengh spectrophotometry combined with a spectral mapping technique (SPM) and by reversed-phase high-performance liquid chromatography. The highest (10-fold) concentration of pigments was achieved on octadecylsilica sorbent. It can be used five times without losing adsorption and desorption characteristics. SPM indicated that multiwavelength spectrophotometry can be employed for the differentiation of red wines. Comparison of the chromatograms of pigments with and without preconcentration showed that preconcentration makes possible the separation and detection of pigments present in low concentration in red wines.

Recent progress of task-specific ionic liquids in chiral resolution and extraction of biological samples and metal ions.

PubMed

Wu, Datong; Cai, Pengfei; Zhao, Xiaoyong; Kong, Yong; Pan, Yuanjiang

2018-01-01

Ionic liquids have been functionalized for modern applications. The functional ionic liquids are also called task-specific ionic liquids. Various task-specific ionic liquids with certain groups have been constructed and exploited widely in the field of separation. To take advantage of their properties in separation science, task-specific ionic liquids are generally used in techniques such as liquid-liquid extraction, solid-phase extraction, gas chromatography, high-performance liquid chromatography, and capillary electrophoresis. This review mainly covers original research papers published in the last five years, and we will focus on task-specific ionic liquids as the chiral selectors in chiral resolution and as extractant or sensor for biological samples and metal ion purification. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nucleophosmin integrates within the nucleolus via multi-modal interactions with proteins displaying R-rich linear motifs and rRNA

PubMed Central

Mitrea, Diana M; Cika, Jaclyn A; Guy, Clifford S; Ban, David; Banerjee, Priya R; Stanley, Christopher B; Nourse, Amanda; Deniz, Ashok A; Kriwacki, Richard W

2016-01-01

The nucleolus is a membrane-less organelle formed through liquid-liquid phase separation of its components from the surrounding nucleoplasm. Here, we show that nucleophosmin (NPM1) integrates within the nucleolus via a multi-modal mechanism involving multivalent interactions with proteins containing arginine-rich linear motifs (R-motifs) and ribosomal RNA (rRNA). Importantly, these R-motifs are found in canonical nucleolar localization signals. Based on a novel combination of biophysical approaches, we propose a model for the molecular organization within liquid-like droplets formed by the N-terminal domain of NPM1 and R-motif peptides, thus providing insights into the structural organization of the nucleolus. We identify multivalency of acidic tracts and folded nucleic acid binding domains, mediated by N-terminal domain oligomerization, as structural features required for phase separation of NPM1 with other nucleolar components in vitro and for localization within mammalian nucleoli. We propose that one mechanism of nucleolar localization involves phase separation of proteins within the nucleolus. DOI: http://dx.doi.org/10.7554/eLife.13571.001 PMID:26836305

Purification of lignans from Fructus Arctii using off-line two-dimensional supercritical fluid chromatography/reversed-phase liquid chromatography.

PubMed

Yang, Bichao; Xin, Huaxia; Wang, Feier; Cai, Jianfeng; Liu, Yanfang; Fu, Qing; Jin, Yu; Liang, Xinmiao

2017-08-01

As a common traditional Chinese medicine, Fructus Arctii has important clinical medical values. Its main components are lignans, which are difficult to separate and analyze because of the complex composition, similar chemical structures, and close properties. In this study, an off-line two-dimensional supercritical fluid chromatography/reversed-phase liquid chromatography method, as well as an effective sample pretreatment method based on hydrophilic interaction chromatography material, was developed to enrich the minor lignan fractions and obtain high-purity compounds. In total, 12 high-purity compounds were isolated from Fructus Arctii. Their structures were identified by using high-resolution mass spectrometry and nuclear magnetic resonance spectroscopy, which showed that all were lignans and that most of them were isomers. The results demonstrated the effective off-line two-dimensional supercritical fluid chromatography/reversed-phase liquid chromatography method for the purification of lignans from Fructus Arctii. The separation protocol established here will be beneficial for the separation of complex samples from other kinds of natural products. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Perturbation theory of structure in classical liquid mixtures: Application to metallic systems near phase separation. Ph.D. Thesis

NASA Technical Reports Server (NTRS)

Henderson, R. L.

1974-01-01

The partial structure factors of classical simple liquid mixtures near phase separation are dicussed. The theory is developed for particles interacting through pair potentials, and is thus appropriate both to insulating fluids, and also to metallic systems if these may be described by an effective ion-ion pair interaction. The motivation arose from consideration of metallic liquid mixtures, in which resistive anomalies have been observed near phase separation. A mean field theory correction appropriate to 3 pair potential for the effects of correlated motions in the reference fluid is studied. The work is cast in terms of functions which are closely related to the direct correlation functions of Ornstein and Zernike. The results are qualitatively in accord with physical expectations. Quantitative agreement with experiment seems to turn on the selection of the hard core reference potential in terms of the metallic effective pair potential. It is suggested that the present effective pair potentials are perhaps not properly used to calculate the metallic structure factors at long wavelength.

Nucleophosmin integrates within the nucleolus via multi-modal interactions with proteins displaying R-rich linear motifs and rRNA

DOE PAGES

Mitrea, Diana M.; Cika, Jaclyn A.; Guy, Clifford S.; ...

2016-02-02

In this study, the nucleolus is a membrane-less organelle formed through liquid-liquid phase separation of its components from the surrounding nucleoplasm. Here, we show that nucleophosmin (NPM1) integrates within the nucleolus via a multi-modal mechanism involving multivalent interactions with proteins containing arginine-rich linear motifs (R-motifs) and ribosomal RNA (rRNA). Importantly, these R-motifs are found in canonical nucleolar localization signals. Based on a novel combination of biophysical approaches, we propose a model for the molecular organization within liquid-like droplets formed by the N-terminal domain of NPM1 and R-motif peptides, thus providing insights into the structural organization of the nucleolus. We identifymore » multivalency of acidic tracts and folded nucleic acid binding domains, mediated by N-terminal domain oligomerization, as structural features required for phase separation of NPM1 with other nucleolar components in vitro and for localization within mammalian nucleoli. We propose that one mechanism of nucleolar localization involves phase separation of proteins within the nucleolus.« less

Subzero-Temperature Liquid-Liquid Extraction Coupled with UPLC-MS-MS for the Simultaneous Determination of 12 Bioactive Components in Traditional Chinese Medicine Gegen-Qinlian Decoction.

PubMed

Shi, Zhihong; Li, Zhimin; Zhang, Shulan; Fu, Hongna; Zhang, Hongyi

2015-09-01

Based on the phase separation phenomenon of acetonitrile-water system at subzero temperature, a subzero-temperature liquid-liquid extraction coupled with ultra-performance liquid chromatography tandem quadrupole mass spectrometry : UPLC-MS-MS) method was developed for the simultaneous determination of 12 bioactive components in Gegen-Qinlian decoction. After optimization, the extraction conditions were set as follows: 3.0 mL of aqueous sample solution (pH 5.86) was extracted with 2 mL of acetonitrile at -35°C for 35 min. The separated acetonitrile phase was diluted 10-fold with water before UPLC-MS-MS analysis. Separation was performed on a Waters ACQUITY UPLC(®)BEH C18 column (2.1 × 100 mm i.d., 1.7 µm) with ammonium formate buffer solution (20 mmol L(-1), pH 3.2, adjusted by formic acid) and acetonitrile as mobile phase with gradient elution. Twelve target components could be separated within 10 min and quantified in multiple reaction monitoring mode, both positive and negative ionization modes were employed. Limits of detection were in the range of 0.0003-0.0451 μg mL(-1). Relative standard deviation values for intra- and interday precision were <2.71 and 8.94%, respectively. The established method provides a simple and effective framework for the quality control of Gegen-Qinlian decoction and related traditional Chinese medicinal preparations. © The Author 2015. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

CARBON DIOXIDE SEPARATION BY PHASE ENHANCED GAS-LIQUID ABSORPTION

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

Liang Hu

A new process called phase enhanced gas-liquid absorption has been developed in its early stage. It was found that adding another phase into the absorption system of gas/aqueous phase could enhance the absorption rate. A system with three phases was studied. In the system, gas phase was carbon dioxide. Two liquid phases were used. One was organic phase. Another was aqueous phase. By addition of organic phase into the absorption system of CO{sub 2}-aqueous phase, the absorption rate of CO{sub 2} was increased significantly. CO{sub 2} finally accumulated into aqueous phase. The experimental results proved that (1) Absorption rate ofmore » carbon dioxide was enhanced by adding organic phase into gas aqueous phase system; (2) Organic phase played the role of transportation of gas solute (CO{sub 2}). Carbon dioxide finally accumulated into aqueous phase.« less

Ionic liquid compatibility in polyethylene oxide/siloxane ion gel membranes

DOE PAGES

Kusuma, Victor A.; Macala, Megan K.; Liu, Jian; ...

2018-10-02

Ion gel films were prepared by incorporating eight commercially available ionic liquids in two different cross-linked polymer matrices to evaluate their phase miscibility, gas permeability and ionic conductivity for potential applications as gas separation membranes and solid electrolyte materials. The ionic liquids cations were 1-ethyl-3-methylimidazolium, 1-ethyl-3-methylpyridinium, 1-butyl-1-methylpyrrolidinium, tributylmethylphosphonium, and butyltrimethylammonium with a common anion (bis(trifluoromethylsulfonyl)imide). In addition, ionic liquids with 1-ethyl-3-methylimidazolium cation with acetate, dicyanamide and tetrafluoroborate counterions were evaluated. The two polymers were cross-linked poly(ethylene oxide) and cross-linked poly(ethylene oxide)/siloxane copolymer. Differential scanning calorimetry, X-ray diffractometry and visual observations were performed to evaluate the ion gels’ miscibility, thermal stabilitymore » and homogeneity. Ionic liquids with the least basic anion (bis(trifluoromethylsulfonyl)imide) and aromatic cations containing acidic proton (e.g. imidazolium and pyridinium) gave the most stable and miscible ion gels. Phase stability was shown to be a function of both ionic liquid content and temperature, with phase separation observed at elevated temperatures. In conclusion, gas permeability testing with carbon dioxide and nitrogen and ionic conductivity measurements confirmed that these ionic liquids increased the gas permeability and ionic conductivity of the polymers.« less

Ionic liquid compatibility in polyethylene oxide/siloxane ion gel membranes

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

Kusuma, Victor A.; Macala, Megan K.; Liu, Jian

Ion gel films were prepared by incorporating eight commercially available ionic liquids in two different cross-linked polymer matrices to evaluate their phase miscibility, gas permeability and ionic conductivity for potential applications as gas separation membranes and solid electrolyte materials. The ionic liquids cations were 1-ethyl-3-methylimidazolium, 1-ethyl-3-methylpyridinium, 1-butyl-1-methylpyrrolidinium, tributylmethylphosphonium, and butyltrimethylammonium with a common anion (bis(trifluoromethylsulfonyl)imide). In addition, ionic liquids with 1-ethyl-3-methylimidazolium cation with acetate, dicyanamide and tetrafluoroborate counterions were evaluated. The two polymers were cross-linked poly(ethylene oxide) and cross-linked poly(ethylene oxide)/siloxane copolymer. Differential scanning calorimetry, X-ray diffractometry and visual observations were performed to evaluate the ion gels’ miscibility, thermal stabilitymore » and homogeneity. Ionic liquids with the least basic anion (bis(trifluoromethylsulfonyl)imide) and aromatic cations containing acidic proton (e.g. imidazolium and pyridinium) gave the most stable and miscible ion gels. Phase stability was shown to be a function of both ionic liquid content and temperature, with phase separation observed at elevated temperatures. In conclusion, gas permeability testing with carbon dioxide and nitrogen and ionic conductivity measurements confirmed that these ionic liquids increased the gas permeability and ionic conductivity of the polymers.« less

Thermoresponsive light scattering device utilizing surface behavior effects between polyimide and an ionic liquid-water mixture exhibiting lower critical solution temperature (LCST)-type phase separation

NASA Astrophysics Data System (ADS)

Goda, Kazuya; Takatoh, Kohki; Funasako, Yusuke; Inokuchi, Makoto

2018-06-01

We proposed a thermoresponsive light scattering device that utilizes the surface behavior between polyimide and an ionic liquid-water mixture exhibiting lower critical solution temperature (LCST)-type phase separation. The LCST behavior for an ionic liquid device utilizing the polyimide with and without alkyl side chains was investigated. In the here-reported ionic liquid device that utilized the polyimide with alkyl side chains, [nBu4P][CF3COO] droplets were generated by phase separation—they were predominantly formed at the alkyl surface by a surface pinning effect. A stable transmittance in the opaque state could be obtained with this device. In contrast, an ionic liquid device using polyimide without alkyl side chains deteriorated transmittance in the opaque state because there was no surface pinning effect. Additionally, the viewing angle, contrast ratio, and heat cycle testing of this ionic liquid device with polyimide with alkyl side chains were also investigated. The results indicated that no parallax was obtained and that the ionic liquid device has a stable transmittance (verified by heat cycle testing). This unique device is expected to find use in the smart window applications that are activated by temperature changes.

On-Chip Microfluidic Components for In Situ Analysis, Separation, and Detection of Amino Acids

NASA Technical Reports Server (NTRS)

Zheng, Yun; Getty, Stephanie; Dworkin, Jason; Balvin, Manuel; Kotecki, Carl

2013-01-01

The Astrobiology Analytical Laboratory at GSFC has identified amino acids in meteorites and returned cometary samples by using liquid chromatography-electrospray ionization time-of-flight mass spectrometry (LCMS). These organic species are key markers for life, having the property of chirality that can be used to distinguish biological from non-biological amino acids. One of the critical components in the benchtop instrument is liquid chromatography (LC) analytical column. The commercial LC analytical column is an over- 250-mm-long and 4.6-mm-diameter stainless steel tube filled with functionized microbeads as stationary phase to separate the molecular species based on their chemistry. Miniaturization of this technique for spaceflight is compelling for future payloads for landed missions targeting astrobiology objectives. A commercial liquid chromatography analytical column consists of an inert cylindrical tube filled with a stationary phase, i.e., microbeads, that has been functionalized with a targeted chemistry. When analyte is sent through the column by a pressurized carrier fluid (typically a methanol/ water mixture), compounds are separated in time due to differences in chemical interactions with the stationary phase. Different species of analyte molecules will interact more strongly with the column chemistry, and will therefore take longer to traverse the column. In this way, the column will separate molecular species based on their chemistry. A lab-on-chip liquid analysis tool was developed. The microfluidic analytical column is capable of chromatographically separating biologically relevant classes of molecules based on their chemistry. For this analytical column, fabrication, low leak rate, and stationary phase incorporation of a serpentine microchannel were demonstrated that mimic the dimensions of a commercial LC column within a 5 10 1 mm chip. The microchannel in the chip has a 75- micrometer-diameter oval-shaped cross section. The serpentine microchannel has four different lengths: 40, 60, 80, and 100 mm. Functionized microbeads were filled inside the microchannel to separate molecular species based on their chemistry.

Liquid-liquid two phase systems for the production of porous hydrogels and hydrogel microspheres for biomedical applications: A tutorial review

PubMed Central

Elbert, Donald L.

2010-01-01

Macroporous hydrogels may have direct applications in regenerative medicine as scaffolds to support tissue formation. Hydrogel microspheres may be used as drug delivery vehicles or as building blocks to assemble modular scaffolds. A variety of techniques exist to produce macroporous hydrogels and hydrogel microspheres. A subset of these relies on liquid-liquid two phase systems. Within this subset, vastly different types of polymerization processes are found. In this review, the history, terminology and classification of liquid-liquid two phase polymerization and crosslinking are described. Instructive examples of hydrogel microsphere and macroporous scaffold formation by precipitation/dispersion, emulsion and suspension polymerizations are used to illustrate the nature of these processes. The role of the kinetics of phase separation in determining the morphology of scaffolds and microspheres is also delineated. Brief descriptions of miniemulsion, microemulsion polymerization and ionotropic gelation are also included. PMID:20659596

Phase change in liquid face seals

NASA Technical Reports Server (NTRS)

Hughes, W. F.; Winowich, N. S.; Birchak, M. J.; Kennedy, W. C.

1978-01-01

A study is made of boiling (or phase change) in liquid face seals. An appropriate model is set up and approximate solutions obtained. Some practical illustrative examples are given. Major conclusions are that (1) boiling may occur more often than has been suspected particularly when the sealed liquid is near saturation conditions, (2) the temperature variation in a seal clearance region may not be very great and the main reason for boiling is the flashing which occurs as the pressure decreases through the seal clearance, and (3) there are two separate values of the parameter film-thickness/angular-velocity-squared (and associated radii where phase change takes place) which provide the same separating force under a given set of operating conditions. For a given speed seal face excursions about the larger spacing are stable, but excursions about the smaller spacing are unstable, leading to a growth to the larger spacing or a catastrophic collapse.

Synthesis of cellulose-2,3-bis(3,5-dimethylphenylcarbamate) in an ionic liquid and its chiral separation efficiency as stationary phase.

PubMed

Liu, Runqiang; Zhang, Yijun; Bai, Lianyang; Huang, Mingxian; Chen, Jun; Zhang, Yuping

2014-04-11

A chiral selector of cellulose-2,3-bis(3,5-dimethylphenylcarbamate) (CBDMPC) was synthesized by reacting 3,5-dimethylphenyl isocyanate with microcrystalline cellulose dissolved in an ionic liquid of 1-allyl-3-methyl-imidazolium chloride (AMIMCl). The obtained chiral selector was effectively characterized by infrared spectroscopy, elemental analysis and 1H NMR. The selector was reacted with 3-aminopropylsilanized silica gel and the CBDMPC bonded chiral stationary phase (CSP) was obtained. Chromatographic evaluation of the prepared CSPs was conducted by high performance liquid chromatographic (HPLC) and baseline separation of three typical fungicides including hexaconazole, metalaxyl and myclobutanil was achieved using n-hexane/isopropanol as the mobile phase with a flow rate 1.0 mL/min. Experimental results also showed that AMIMCl could be recycled easily and reused in the preparation of CSPs as an effective reaction media.

Synthesis of Cellulose-2,3-bis(3,5-dimethylphenylcarbamate) in an Ionic Liquid and Its Chiral Separation Efficiency as Stationary Phase

PubMed Central

Liu, Runqiang; Zhang, Yijun; Bai, Lianyang; Huang, Mingxian; Chen, Jun; Zhang, Yuping

2014-01-01

A chiral selector of cellulose-2,3-bis(3,5-dimethylphenylcarbamate) (CBDMPC) was synthesized by reacting 3,5-dimethylphenyl isocyanate with microcrystalline cellulose dissolved in an ionic liquid of 1-allyl-3-methyl-imidazolium chloride (AMIMCl). The obtained chiral selector was effectively characterized by infrared spectroscopy, elemental analysis and 1H NMR. The selector was reacted with 3-aminopropylsilanized silica gel and the CBDMPC bonded chiral stationary phase (CSP) was obtained. Chromatographic evaluation of the prepared CSPs was conducted by high performance liquid chromatographic (HPLC) and baseline separation of three typical fungicides including hexaconazole, metalaxyl and myclobutanil was achieved using n-hexane/isopropanol as the mobile phase with a flow rate 1.0 mL/min. Experimental results also showed that AMIMCl could be recycled easily and reused in the preparation of CSPs as an effective reaction media. PMID:24733066

In situ creation of reactive polymer nanoparticles and resulting polymer layers formed at the interfaces of liquid crystals (Conference Presentation)

NASA Astrophysics Data System (ADS)

Kang, Shin-Woong; Kundu, Sudarshan; Park, Heung-Shik; Oh, Keun Chan; Lyu, Jae Jin

2017-02-01

We report the in situ creation of reactive polymer nanoparticles and resulting polymer networks formed at the interfaces of liquid crystals. It is known that polymerization-induced phase separation proceeds in two distinct regimes depending on the concentration of monomer. For a high monomer concentration, phase separation occurs mainly through the spinodal decomposition process, consequently resulting in interpenetrating polymer networks. For a dilute system, however, the phase separation mainly proceeds and completes in the binodal decomposition regime. The system resembles the aggregation process of colloidal particle. In this case, the reaction kinetics is limited by the reaction between in situ created polymer aggregates and hence the network morphologies are greatly influenced by the diffusion of reactive polymer particles. The thin polymer layers localized at the surface of substrate are inevitably observed and can be comprehended by the interfacial adsorption and further cross-linking reaction of reactive polymer aggregates at the interface. This process provides a direct perception on understanding polymer stabilized liquid crystals accomplished by the interfacial polymer layer. The detailed study has been performed for an extremely dilute condition (below 0.5 wt%) by employing systematic experimental approaches. Creation and growth of polymer nanoparticles have been measured by particle size analyzer. The interfacial localization of polymer aggregates and resulting interfacial layer formation with a tens of nanometer scale have been exploited at various interfaces such as liquid-solid, liquid-liquid, and liquid-gas interfaces. The resulting interfacial layers have been characterized by using fuorescent confocal microscope and field emission scanning electron microscope. The detailed processes of the polymer stabilized vertically aligned liquid crystals will be discussed in support of the reported study.

Efficient chemical potential evaluation with kinetic Monte Carlo method and non-uniform external potential: Lennard-Jones fluid, liquid, and solid

NASA Astrophysics Data System (ADS)

Ustinov, E. A.

2017-07-01

The aim of this paper is to present a method of a direct evaluation of the chemical potential of fluid, liquid, and solid with kinetic Monte Carlo simulation. The method is illustrated with the 12-6 Lennard-Jones (LJ) system over a wide range of density and temperature. A distinctive feature of the methodology used in the present study is imposing an external potential on the elongated simulation box to split the system into two equilibrium phases, one of which is substantially diluted. This technique provides a reliable direct evaluation of the chemical potential of the whole non-uniform system (including that of the uniformly distributed dense phase in the central zone of the box), which, for example, is impossible in simulation of the uniform crystalline phase. The parameters of the vapor-liquid, liquid-solid, and fluid-solid transitions have been reliably determined. The chemical potential and the pressure are defined as thermodynamically consistent functions of density and temperature separately for the liquid and the solid (FCC) phases. It has been shown that in two-phase systems separated by a flat interface, the crystal melting always occurs at equilibrium conditions. It is also proved that in the limit of zero temperature, the specific heat capacity of an LJ crystal at constant volume is exactly 3Rg (where Rg is the gas constant) without resorting to harmonic oscillators.

Green synthesis of a typical chiral stationary phase of cellulose-tris(3, 5-dimethylphenylcarbamate)

PubMed Central

2013-01-01

Background At present, the study on the homogeneous-phase derivatization of cellulose in ionic liquid is mainly focused on its acetylation. To the best of our knowledge, there has been no such report on the preparation of cellulose-tris(3,5-dimethylphenylcarbamate) (CDMPC) with ionic liquid 1-allyl-3-methyl-imidazolium chloride (AmimCl) so far. Results With ionic liquid 1-allyl-3-methylimidazolium chloride (AmimCl) as a reaction solvent, cellulose-tris(3,5-dimethylphenylcarbamate) (CDMPC) was synthesized by the reaction of 3,5-dimethylphenyl isocyanate and soluble microcrystalline cellulose in a homogeneous phase. The synthesized CDMPC was then coated onto the surfaces of aminopropyl silica gel to prepare a chiral stationary phase (CSP). The prepared CSP was successfully used in chiral separation of seven racemic pesticides by high performance liquid chromatography (HPLC). Good chiral separation was obtained using n-hexane and different modifiers as the mobile phases under the optimal percentage and column temperature, with the resolution of metalaxyl, diniconazole, flutriafol, paclobutrazol, hexaconazole, myclobutanil and hexythiazox of 1.73, 1.56, 1.26, 1.00, 1.18, 1.14 and 1.51, respectively. The experimental results suggested it was a good choice using a green solvent of AmimCl for cellulose functionalization. Conclusion CDMPC was successfully synthesized as the chiral selector by reacting 3, 5-dimethylphenyl isocyanate with dissolved microcrystalline cellulose in a green ionic liquid of AmimCl. PMID:23890199

Computer code for gas-liquid two-phase vortex motions: GLVM

NASA Technical Reports Server (NTRS)

Yeh, T. T.

1986-01-01

A computer program aimed at the phase separation between gas and liquid at zero gravity, induced by vortex motion, is developed. It utilizes an explicit solution method for a set of equations describing rotating gas-liquid flows. The vortex motion is established by a tangential fluid injection. A Lax-Wendroff two-step (McCormack's) numerical scheme is used. The program can be used to study the fluid dynamical behavior of the rotational two-phase fluids in a cylindrical tank. It provides a quick/easy sensitivity test on various parameters and thus provides the guidance for the design and use of actual physical systems for handling two-phase fluids.

[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.

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.

Contact Angle Influence on Geysering Jets in Microgravity Investigated

NASA Technical Reports Server (NTRS)

Chato, David J.

2004-01-01

Microgravity poses many challenges to the designer of spacecraft tanks. Chief among these are the lack of phase separation and the need to supply vapor-free liquid or liquid-free vapor to the spacecraft processes that require fluid. One of the principal problems of phase separation is the creation of liquid jets. A jet can be created by liquid filling, settling of the fluid to one end of the tank, or even closing a valve to stop the liquid flow. Anyone who has seen a fountain knows that jets occur in normal gravity also. However, in normal gravity, the gravity controls and restricts the jet flow. In microgravity, with gravity largely absent, surface tension forces must be used to contain jets. To model this phenomenon, a numerical method that tracks the fluid motion and the surface tension forces is required. Jacqmin has developed a phase model that converts the discrete surface tension force into a barrier function that peaks at the free surface and decays rapidly away. Previous attempts at this formulation were criticized for smearing the interface. This can be overcome by sharpening the phase function, double gridding the fluid function, and using a higher-order solution for the fluid function. The solution of this equation can be rewritten as two coupled Poisson equations that also include the velocity.

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.

Fine-scale Horizontal Structure of Arctic Mixed-Phase Clouds.

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

Rambukkange,M.; Verlinde, J.; Elorante, E.

2006-07-10

Recent in situ observations in stratiform clouds suggest that mixed phase regimes, here defined as limited cloud volumes containing both liquid and solid water, are constrained to narrow layers (order 100 m) separating all-liquid and fully glaciated volumes (Hallett and Viddaurre, 2005). The Department of Energy Atmospheric Radiation Measurement Program's (DOE-ARM, Ackerman and Stokes, 2003) North Slope of Alaska (NSA) ARM Climate Research Facility (ACRF) recently started collecting routine measurement of radar Doppler velocity power spectra from the Millimeter Cloud Radar (MMCR). Shupe et al. (2004) showed that Doppler spectra has potential to separate the contributions to the total reflectivitymore » of the liquid and solid water in the radar volume, and thus to investigate further Hallett and Viddaurre's findings. The Mixed-Phase Arctic Cloud Experiment (MPACE) was conducted along the NSA to investigate the properties of Arctic mixed phase clouds (Verlinde et al., 2006). We present surface based remote sensing data from MPACE to discuss the fine-scale structure of the mixed-phase clouds observed during this experiment.« less

Further development of a robust workup process for solution-phase high-throughput library synthesis to address environmental and sample tracking issues.

PubMed

Kuroda, Noritaka; Hird, Nick; Cork, David G

2006-01-01

During further improvement of a high-throughput, solution-phase synthesis system, new workup tools and apparatus for parallel liquid-liquid extraction and evaporation have been developed. A combination of in-house design and collaboration with external manufacturers has been used to address (1) environmental issues concerning solvent emissions and (2) sample tracking errors arising from manual intervention. A parallel liquid-liquid extraction unit, containing miniature high-speed magnetic stirrers for efficient mixing of organic and aqueous phases, has been developed for use on a multichannel liquid handler. Separation of the phases is achieved by dispensing them into a newly patented filter tube containing a vertical hydrophobic porous membrane, which allows only the organic phase to pass into collection vials positioned below. The vertical positioning of the membrane overcomes the hitherto dependence on the use of heavier-than-water, bottom-phase, organic solvents such as dichloromethane, which are restricted due to environmental concerns. Both small (6-mL) and large (60-mL) filter tubes were developed for parallel phase separation in library and template synthesis, respectively. In addition, an apparatus for parallel solvent evaporation was developed to (1) remove solvent from the above samples with highly efficient recovery and (2) avoid the movement of individual samples between their collection on a liquid handler and registration to prevent sample identification errors. The apparatus uses a diaphragm pump to achieve a dynamic circulating closed system with a heating block for the rack of 96 sample vials and an efficient condenser to trap the solvents. Solvent recovery is typically >98%, and convenient operation and monitoring has made the apparatus the first choice for removal of volatile solvents.

N-linked glycoprotein analysis using dual-extraction ultrahigh-performance liquid chromatography and electrospray tandem mass spectrometry.

PubMed

Siu, S O; Lam, Maggie P Y; Lau, Edward; Yeung, William S B; Cox, David M; Chu, Ivan K

2010-01-01

Although reverse-phase liquid chromatography (RP-LC) is a common technique for peptide separation in shotgun proteomics and glycoproteomics, it often provides unsatisfactory results for the analysis of glycopeptides and glycans. This bias against glycopeptides makes it difficult to study glycoproteins. By coupling mass spectrometry (MS) with a combination of RP-LC and normal-phase (NP)-LC as an integrated front-end separation system, we demonstrate that effective identification and characterization of both peptides and glycopeptides mixtures, and their constituent glycan structures, can be achieved from a single sample injection event.

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.

Boundary of Phase Co-existence in Docosahexaenoic Acid System

NASA Astrophysics Data System (ADS)

Lor, Chai; Hirst, Linda S.

2011-11-01

Docosahexaenoic acid (DHA) is a highly polyunsaturated fatty acid (PUFA) that exhibits six double bonds in the hydrocarbon tail. It induces phase separation of the membrane into liquid order and liquid disorder in mixtures containing other lipids with more saturation and cholesterol. With the utilization of atomic force microscopy, phase co-existence is observed in lipid mixtures containing DHA on a single supported lipid bilayer. The boundary of phase co-existence with decreasing DHA concentration is explored. The elastic force, thickness, and roughness of the different phases are investigated.

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.

Modeling Gas-Particle Partitioning of SOA: Effects of Aerosol Physical State and RH

NASA Astrophysics Data System (ADS)

Zuend, A.; Seinfeld, J.

2011-12-01

Aged tropospheric aerosol particles contain mixtures of inorganic salts, acids, water, and a large variety of organic compounds. In liquid aerosol particles non-ideal mixing of all species determines whether the condensed phase undergoes liquid-liquid phase separation or whether it is stable in a single mixed phase, and whether it contains solid salts in equilibrium with their saturated solution. The extended thermodynamic model AIOMFAC is able to predict such phase states by representing the variety of organic components using functional groups within a group-contribution concept. The number and composition of different condensed phases impacts the diversity of reaction media for multiphase chemistry and the gas-particle partitioning of semivolatile species. Recent studies show that under certain conditions biogenic and other organic-rich particles can be present in a highly viscous, semisolid or amorphous solid physical state, with consequences regarding reaction kinetics and mass transfer limitations. We present results of new gas-particle partitioning computations for aerosol chamber data using a model based on AIOMFAC activity coefficients and state-of-the-art vapor pressure estimation methods. Different environmental conditions in terms of temperature, relative humidity (RH), salt content, amount of precursor VOCs, and physical state of the particles are considered. We show how modifications of absorptive and adsorptive gas-particle mass transfer affects the total aerosol mass in the calculations and how the results of these modeling approaches compare to data of aerosol chamber experiments, such as alpha-pinene oxidation SOA. For a condensed phase in a mixed liquid state containing ammonium sulfate, the model predicts liquid-liquid phase separation up to high RH in case of, on average, moderately hydrophilic organic compounds, such as first generation oxidation products of alpha-pinene. The computations also reveal that treating liquid phases as ideal mixtures substantially overestimates the SOA mass, especially at high relative humidity.

Evaluation and application of a mixed-mode chromatographic stationary phase in two-dimensional liquid chromatography for the separation of traditional Chinese medicine.

PubMed

Wei, Zhishen; Fu, Qing; Cai, Jianfeng; Huan, Liyun; Zhao, Jianchao; Shi, Hui; Jin, Yu; Liang, Xinmiao

2016-06-01

In this study, two mixed-mode chromatography stationary phases (C8SAX and C8SCX) were evaluated and used to establish a two-dimensional liquid chromatography system for the separation of traditional Chinese medicine. The chromatographic properties of the mixed-mode columns were systematically evaluated by comparing with other three columns of C8, strong anion exchanger, and strong cation exchanger. The result showed that C8SAX and C8SCX had a mixed-mode retention mechanism including electrostatic interaction and hydrophobic interaction. Especially, they were suitable for separating acidic and/or basic compounds and their separation selectivities could be easily adjusted by changing pH value. Then, several off-line 2D-LC systems based on the C8SAX in the first dimension and C8SAX, C8SCX, or C8 columns in the second dimension were developed to analyze a traditional Chinese medicine-Uncaria rhynchophylla. The two-dimensional liquid chromatography system of C8SAX (pH 3.0) × C8SAX (pH 6.0) exhibited the most effective peak distribution. Finally, fractions of U. rhynchophylla prepared from the first dimension were successfully separated on the C8SAX column with a gradient pH. Thus, the mixed-mode stationary phase could provide a platform to separate the traditional Chinese medicine in practical applications. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

STRIPPING OF URANIUM FROM ORGANIC EXTRACTANTS

DOEpatents

Crouse, D.J. Jr.

1962-09-01

A liquid-liquid extraction method is given for recovering uranium values from uranium-containing solutions. Uranium is removed from a uranium-containing organic solution by contacting said organic solution with an aqueous ammonium carbonate solution substantially saturated in uranium values. A uranium- containing precipitate is thereby formed which is separated from the organic and aqueous phases. Uranium values are recovered from this separated precipitate. (AE C)

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.

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

Wu, H.L.; Spronsen, G. van; Klaus, E.H.

A simulation model of the dynamics of a by-pass pig and related two-phase flow behavior along with field trials of the pig in a dry-gas pipeline have revealed significant gains in use of a by-pass pig in modifying gas and liquid production rates. The method can widen the possibility of applying two-phase flow pipeline transportation to cases in which separator or slug-catcher capacity is limited by practicality or cost. Pigging two-phase pipelines normally generates large liquid slug volumes in front of the pig. These require large separators or slug catchers. Using a high by-pass pig to disperse the liquid andmore » reduce the maximum liquid production rate before pig arrival has been investigated by Shell Exploration and Production companies. A simulation model of the dynamics of the pig and related two-phase flow behavior in the pipeline was used to predict the performance of by-pass pigs. Field trials in a dry-gas pipeline were carried out to provide friction data and to validate the model. The predicted mobility of the high by-pass pig in the pipeline and risers was verified and the beneficial effects due to the by-pass concept exceeded the prediction of the simplified model.« less

Micro- and Nano-Liquid Phases Coexistent with Ice as Separation and Reaction Media.

PubMed

Okada, Tetsuo

2017-04-01

Ice has a variety of scientifically interesting features, some of which have not been reasonably interpreted despite substantial efforts by researchers. Most chemical studies of ice have focused on the elucidation of its physicochemical nature and its roles in the natural environment. Ice often contains impurities, such as salts, and in such cases, a liquid phase coexists with solid ice over a wide temperature range. This impure ice also acts as a cryoreactor, governing the circulation of chemical species of environmental importance. Reactions and phenomena occurring in this liquid phase show features different from those seen in normal bulk aqueous solutions. In the present account, we discuss the chemical characteristics of the liquid phase that develops in a frozen aqueous phase and show how novel analytical systems can be designed based on he features of the liquid phase which are predictable in some cases but unpredictable in others. © 2017 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Purification of inkjet ink from water using liquid phase, electric discharge polymerization and cellulosic membrane filtration.

PubMed

Jordan, Alexander T; Hsieh, Jeffery S; Lee, Daniel T

2013-01-01

A method to separate inkjet ink from water was developed using a liquid phase, electric discharge process. The liquid phase, electric discharge process with filtration or sedimentation was shown to remove 97% of inkjet ink from solutions containing between 0.1-0.8 g/L and was consistent over a range of treatment conditions. Additionally, particle size analysis of treated allyl alcohol and treated propanol confirmed the electric discharge treatment has a polymerization mechanism, and small molecule analysis of treated methanol using gas chromatography and mass spectroscopy confirmed the mechanism was free radical initiated polymerization.

Simultaneous analysis of tert-butylhydroquinone, tert-butylquinone, butylated hydroxytoluene, 2-tert-butyl-4-hydroxyanisole, 3-tert-butyl-4-hydroxyanisole, α-tocopherol, γ-tocopherol, and δ-tocopherol in edible oils by normal-phase high performance liquid chromatography.

PubMed

Li, Jun; Bi, Yanlan; Sun, Shangde; Peng, Dan

2017-11-01

A normal-phase high performance liquid chromatography method for the simultaneous determination of tert-butylhydroquinone, tert-butylquinone, butylated hydroxytoluene, 2-tert-butyl-4-hydroxyanisole, 3-tert-butyl-4-hydroxyanisole, α-tocopherol, γ-tocopherol, and δ-tocopherol in edible oils was investigated. A silica column was used to separate the analytes with the gradient elution. An ultraviolet-visible detector was set at dual wavelengths mode (280 and 310nm). The column temperature was 30°C. The analytes were directly extracted with methanol. Results showed that the normal-phase high performance liquid chromatography method performed well with wide liner ranges (0.10∼500.00μg/mL, R 2 >0.9998), low limits of detection and quantitation (below 0.40 and 1.21μg/mL, respectively), and good recoveries (81.38∼102.34% in soybean oils and 83.03∼100.79% in lard, respectively). The reduction of tert-butylquinone caused by the reverse-phase high performance liquid chromatography during the injection was avoided with the current normal-phase method. The two isomers of butylated hydroxyanisole can also be separated with good resolution. Copyright © 2017 Elsevier Ltd. All rights reserved.

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.

High-performance liquid chromatographic determination of loxoprofen and its diastereomeric alcohol metabolites in biological fluids by fluorescence labelling with 4-bromomethyl-6,7-methylenedioxycoumarin.

PubMed

Naganuma, H; Kawahara, Y

1990-09-14

A simple and sensitive high-performance liquid chromatographic procedure to determine loxoprofen and its diastereomeric alcohol metabolites in biological specimens is described. The analysis involves liquid-liquid extraction with benzene, pre-column derivatization with a highly fluorogenic reagent, 4-bromomethyl-6,7-methylenedioxycoumarin (BrMDC) and subsequent separation on a reversed-phase column. Loxoprofen, its pharmacologically active metabolite, trans-alcohol, and less active cis-alcohol were completely separated within 20 min with a mobile phase of 55% of aqueous acetonitrile containing acetic acid. Any endogenous substances do not interfere in the analysis of either plasma or urine samples. The quantitation limit was 0.01 micrograms/ml for human plasma and 0.05 micrograms/ml for urine. The method was applied to a pharmacokinetic study in healthy human subjects who had received 60 mg of loxoprofen sodium.

Process for removing sulfate anions from waste water

DOEpatents

Nilsen, David N.; Galvan, Gloria J.; Hundley, Gary L.; Wright, John B.

1997-01-01

A liquid emulsion membrane process for removing sulfate anions from waste water is disclosed. The liquid emulsion membrane process includes the steps of: (a) providing a liquid emulsion formed from an aqueous strip solution and an organic phase that contains an extractant capable of removing sulfate anions from waste water; (b) dispersing the liquid emulsion in globule form into a quantity of waste water containing sulfate anions to allow the organic phase in each globule of the emulsion to extract and absorb sulfate anions from the waste water and (c) separating the emulsion including its organic phase and absorbed sulfate anions from the waste water to provide waste water containing substantially no sulfate anions.

Combination of solid phase extraction and dispersive liquid-liquid microextraction for separation/preconcentration of ultra trace amounts of uranium prior to its fiber optic-linear array spectrophotometry determination.

PubMed

Dadfarnia, Shayessteh; Shabani, Ali Mohammad Haji; Shakerian, Farid; Shiralian Esfahani, Golnaz

2013-12-15

A simple and sensitive method for the separation and preconcentration of the ultra trace amounts of uranium and its determination by spectrophotometry was developed. The method is based on the combination of solid phase extraction and dispersive liquid-liquid microextraction. Thus, by passing the sample through the basic alumina column, the uranyl ion and some cations are separated from the sample matrix. The retained uranyl ion along with the cations are eluted with 5 mL of nitric acid (2 mol L(-1)) and after neutralization of the eluent, the extracted uranyl ion is converted to its anionic benzoate complex and is separated from other cations by extraction of its ion pair with malachite green into small volume of chloroform using dispersive liquid-liquid microextraction. The amount of uranium is then determined by the absorption measurement of the extracted ion pair at 621 nm using flow injection spectrophotometry. Under the optimum conditions, with 500 mL of the sample, a preconcentration factor of 1980, a detection limit of 40 ng L(-1), and a relative standard deviation of 4.1% (n=6) at 400 ng L(-1) were obtained. The method was successfully applied to the determination of uranium in mineral water, river water, well water, spring water and sea water samples. Copyright © 2013 Elsevier B.V. All rights reserved.

Preparation and evaluation of silica-UIO-66 composite as liquid chromatographic stationary phase for fast and efficient separation.

PubMed

Yan, Zhiming; Zheng, Jiangnan; Chen, Jinfeng; Tong, Ping; Lu, Minghua; Lin, Zian; Zhang, Lan

2014-10-31

A silica-UIO-66 composite was fabricated by a simple hydrothermal method and then applied as liquid chromatographic stationary phase for fast and efficient separation. X-ray diffraction patterns showed the presence of UIO-66 crystals in the silica-UIO-66 composites; while scanning electron microscope (SEM) images revealed that silica-UIO-66 composites were a homogeneous mixture of silica bead and UIO-66 crystals. A variety of substituted aromatics, chlorobenzene compounds and polycyclic aromatic hydrocarbons (PAHs) were used to evaluate the retention properties of the silica-UIO-66 composite packed column. Under the optimized conditions, baseline separation of ethylbenzene (EB) and styrene was obtained with high resolution and short retention time. In addition, the silica-UIO-66 composite packed column also showed some advantages in separation of positional isomers, with which baseline separation of EB and xylene, chlorotoluene and dichlorobenzene isomers was achieved. Moreover, the retention mechanisms of these compounds were also discussed in detail. The relative standard deviations (RSDs) for the separation of EB and xylene, chlorotoluene and dichlorobenzene isomers, as well as EB and styrene were 0.42-0.9%, 1.0-1.9%, 0.75-2.0%, and 0.9-2.1% for the retention time, peak area, peak height, and half peak width, respectively. The column efficiencies for EB, p-chlorotoluene, p-dichlorobenzene and styrene were 8780, 9060, 9990 and 5130 plates/m. The successful applications suggested high potentials of silica-MOFs composite as stationary phase for fast and efficient liquid chromatography separation. Copyright © 2014 Elsevier B.V. All rights reserved.

Phase Transition Enthalpy Measurements of Organic and Organometallic Compounds and Ionic Liquids. Sublimation, Vaporization, and Fusion Enthalpies from 1880 to 2015. Part 2. C11-C192

NASA Astrophysics Data System (ADS)

Acree, William; Chickos, James S.

2017-03-01

The second part of this compendium concludes with a collection of phase change enthalpies of organic molecules inclusive of C11-C192 reported over the period 1880-2015. Also included are phase change enthalpies including fusion, vaporization, and sublimation enthalpies for organometallic, ionic liquids, and a few inorganic compounds. Paper I of this compendium, published separately, includes organic compounds from C1 to C10 and describes a group additivity method for evaluating solid, liquid, and gas phase heat capacities as well as temperature adjustments of phase changes. Paper II of this compendium also includes an updated version of a group additivity method for evaluating total phase change entropies which together with the fusion temperature can be useful in estimating total phase change enthalpies. Other uses include application in identifying potential substances that either form liquid or plastic crystals or exhibit additional phase changes such as undetected solid-solid transitions or behave anisotropically in the liquid state.

URANIUM DECONTAMINATION WITH RESPECT TO ZIRCONIUM

DOEpatents

Vogler, S.; Beederman, M.

1961-05-01

A process is given for separating uranium values from a nitric acid aqueous solution containing uranyl values, zirconium values and tetravalent plutonium values. The process comprises contacting said solution with a substantially water-immiscible liquid organic solvent containing alkyl phosphate, separating an organic extract phase containing the uranium, zirconium, and tetravalent plutonium values from an aqueous raffinate, contacting said organic extract phase with an aqueous solution 2M to 7M in nitric acid and also containing an oxalate ion-containing substance, and separating a uranium- containing organic raffinate from aqueous zirconium- and plutonium-containing extract phase.

AM363 martensitic stainless steel: A multiphase equation of state

NASA Astrophysics Data System (ADS)

De Lorenzi-Venneri, Giulia; Crockett, Scott D.

2017-01-01

A multiphase equation of state for stainless steel AM363 has been developed within the Opensesame approach and has been entered as material 4295 in the LANL-SESAME Library. Three phases were constructed separately: the low pressure martensitic phase, the austenitic phase and the liquid. Room temperature data and the explicit introduction of a magnetic contribution to the free energy determined the martensitic phase, while shock Hugoniot data was used to determine the austenitic phase and the phase boundaries. More experimental data or First Principles calculations would be useful to better characterize the liquid.

Solvent extraction separation of Th-227 and Ac-225 in room temperature ionic liquids

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

Bell, Jason R; Boll, Rose Ann; Dai, Sheng

2012-01-01

The solvent extractions of Th-227 and Ac-225 from the aqueous phase into ionic liquids (ILs) were investigated by using N,N,N ,N - tetraoctyldiglycolamide (TODGA) or di(2-ethylhexyl)phosphoric acid (HDEHP) as an extractant. Four ionic liquids, 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([C4mim][NTf2]), 1-butyl-3-methylimidazolium bis(perfluoroethanesulfonyl)imide ([C4mim][BETI]), 1-butyl-2,3-trimethyleneimidazolium (trifluoromethanesulfonyl)imide [BuI5][NTf2], and 1-benzyl pyridinium bis(trifluoromethanesulfonyl)imide ([PhCH2Py][NTf2]) were used as extraction solvents for separation of Th-227 and Ac-225 in this study. Excellent extraction efficiencies and selectivities were found for Th-227/Ac-225 when HDEHP was used as an extractant in these ionic liquids. The effects of different extractant concentrations in ionic liquids and acidities of the aqueous phase on extraction efficienciesmore » and selectivities of Th-227/Ac-225 are also presented in this article.« less

Composition inversion in mixtures of binary colloids and polymer

NASA Astrophysics Data System (ADS)

Zhang, Isla; Pinchaipat, Rattachai; Wilding, Nigel B.; Faers, Malcolm A.; Bartlett, Paul; Evans, Robert; Royall, C. Patrick

2018-05-01

Understanding the phase behaviour of mixtures continues to pose challenges, even for systems that might be considered "simple." Here, we consider a very simple mixture of two colloidal and one non-adsorbing polymer species, which can be simplified even further to a size-asymmetrical binary mixture, in which the effective colloid-colloid interactions depend on the polymer concentration. We show that this basic system exhibits surprisingly rich phase behaviour. In particular, we enquire whether such a system features only a liquid-vapor phase separation (as in one-component colloid-polymer mixtures) or whether, additionally, liquid-liquid demixing of two colloidal phases can occur. Particle-resolved experiments show demixing-like behaviour, but when combined with bespoke Monte Carlo simulations, this proves illusory, and we reveal that only a single liquid-vapor transition occurs. Progressive migration of the small particles to the liquid phase as the polymer concentration increases gives rise to composition inversion—a maximum in the large particle concentration in the liquid phase. Close to criticality, the density fluctuations are found to be dominated by the larger colloids.

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.

A Bibliometric Analysis of Research on Supported Ionic Liquid Membranes during the 1995–2015 Period: Study of the Main Applications and Trending Topics

PubMed Central

Abejón, Ricardo; Pérez-Acebo, Heriberto; Garea, Aurora

2017-01-01

A bibliometric analysis based on Scopus database was performed to identify the global research trends related to Supported Ionic Liquid Membranes (SILMs) during the time period from 1995 to 2015. This work tries to improve the understanding of the most relevant research topics and applications. The results from the analysis reveal that only after 2005 the research efforts focused on SILMs became significant, since the references found before that year are scarce. The most important research works on the four main application groups for SILMs defined in this work (carbon dioxide separation, other gas phase separations, pervaporation and liquid phase separations) were summarized in this paper. Carbon dioxide separation appeared as the application that has received by far the most attention according to the research trends during the analysed period. Comments about other significant applications that are gaining attention, such as the employment of SILMs in analytical tasks or their consideration for the production of fuel cells, have been included. PMID:29112172

A resolution approach of racemic phenylalanine with aqueous two-phase systems of chiral tropine ionic liquids.

PubMed

Wu, Haoran; Yao, Shun; Qian, Guofei; Yao, Tian; Song, Hang

2015-10-30

Aqueous two-phase systems (ATPS) based on tropine type chiral ionic liquids and inorganic salt solution were designed and prepared for the enantiomeric separation of racemic phenylalanine. The phase behavior of IL-based ATPS was comprehensive investigated, and phase equilibrium data were correlated by Merchuk equation. Various factors were also systematically investigated for their influence on separation efficiency. Under the appropriate conditions (0.13g/g [C8Tropine]pro, 35mg/g Cu(Ac)2, 20mg/g d,l-phenylalanine, 0.51g/g H2O and 0.30g/g K2HPO4), the enantiomeric excess value of phenylalanine in solid phase (mainly containing l-enantiomer) was 65%. Finally, the interaction mechanism was studied via 1D and 2D NMR. The results indicate that d-enantiomer of phenylalanine interacts more strongly with chiral ILs and Cu(2+) based on the chiral ion-pairs space coordination mechanism, which makes it tend to remain in the top IL-rich phase. By contrast, l-enantiomer is transferred into the solid phase. Above chiral ionic liquids aqueous two-phase systems have demonstrated obvious resolution to racemic phenylalanine and could be promising alterative resolution approach for racemic amino acids in aqueous circumstance. Copyright © 2015. Published by Elsevier B.V.

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.

Comparison of various types of stationary phases in non-aqueous reversed-phase high-performance liquid chromatography-mass spectrometry of glycerolipids in blackcurrant oil and its enzymatic hydrolysis mixture.

PubMed

Lísa, Miroslav; Holcapek, Michal; Sovová, Helena

2009-11-20

The selection of column packing during the development of high-performance liquid chromatography method is a crucial step to achieve sufficient chromatographic resolution of analyzed species in complex mixtures. Various stationary phases are tested in this paper for the analysis of complex mixture of triacylglycerols (TGs) in blackcurrant oil using non-aqueous reversed-phase (NARP) system with acetonitrile-2-propanol mobile phase. Conventional C(18) column in the total length of 45 cm is used for the separation of TGs according to their equivalent carbon number, the number and positions of double bonds and acyl chain lengths. The separation of TGs and their more polar hydrolysis products after the partial enzymatic hydrolysis of blackcurrant oil in one chromatographic run is achieved using conventional C(18) column. Retention times of TGs are reduced almost 10 times without the loss of the chromatographic resolution using ultra high-performance liquid chromatography with 1.7 microm C(18) particles. The separation in NARP system on C(30) column shows an unusual phenomenon, because the retention order of TGs changes depending on the column temperature, which is reported for the first time. The commercial monolithic column modified with C(18) is used for the fast analysis of TGs to increase the sample throughput but at cost of low resolution.

Laser capillary spectrophotometric acquisition of bivariate drop size and concentration data for liquid-liquid dispersion

DOEpatents

Tavlarides, Lawrence L.; Bae, Jae-Heum

1991-01-01

A laser capillary spectrophotometric technique measures real time or near real time bivariate drop size and concentration distribution for a reactive liquid-liquid dispersion system. The dispersion is drawn into a precision-bore glass capillary and an appropriate light source is used to distinguish the aqueous phase from slugs of the organic phase at two points along the capillary whose separation is precisely known. The suction velocity is measured, as is the length of each slug from which the drop free diameter is calculated. For each drop, the absorptivity at a given wavelength is related to the molar concentration of a solute of interest, and the concentration of given drops of the organic phase is derived from pulse heights of the detected light. This technique permits on-line monitoring and control of liquid-liquid dispersion processes.

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.

Facile preparation of a stable and functionalizable hybrid monolith via ring-opening polymerization for capillary liquid chromatography.

PubMed

Lin, Hui; Ou, Junjie; Tang, Shouwan; Zhang, Zhenbin; Dong, Jing; Liu, Zhongshan; Zou, Hanfa

2013-08-02

An organic-inorganic hybrid monolith was prepared by a single-step ring-opening polymerization of octaglycidyldimethylsilyl polyhedral oligomeric silsesquioxane (POSS) with poly(ethylenimine) (PEI). The obtained hybrid monoliths possessed high ordered 3D skeletal microstructure with dual retention mechanism that exhibits reversed-phase (RP) mechanism under polar mobile phase and hydrophilic-interaction liquid chromatography (HILIC) retention mechanism under less polar mobile phase. The high column efficiencies of 110,000N/m can be achieved for separation of alkylbenzenes in capillary reversed-phase liquid chromatography (cLC). Due to the robust property of hybrid monolith and the rich primary and secondary amino groups on its surface, the resulting hybrid monolith was easily modified with γ-gluconolactone and physically coated with cellulose tris(3,5-dimethylphenylcarbamate) (CDMPC), respectively. The former was successfully applied for HILIC separation of neutral, basic and acidic polar compounds as well as small peptides, and the latter for enantioseparation of racemates in cLC. The high column efficiencies were achieved in all of those separations. These results demonstrated that the hybrid monolith (POSS-PEI) possessed high stability and good surface tailorbility, potentially being applied for other research fields. Copyright © 2013 Elsevier B.V. All rights reserved.

Lipid extraction from microalgae using a single ionic liquid

DOEpatents

Salvo, Roberto Di; Reich, Alton; Dykes, Jr., H. Waite H.; Teixeira, Rodrigo

2013-05-28

A one-step process for the lysis of microalgae cell walls and separation of the cellular lipids for use in biofuel production by utilizing a hydrophilic ionic liquid, 1-butyl-3-methylimidazolium. The hydrophilic ionic liquid both lyses the microalgae cell walls and forms two immiscible layers, one of which consists of the lipid contents of the lysed cells. After mixture of the hydrophilic ionic liquid with a suspension of microalgae cells, gravity causes a hydrophobic lipid phase to move to a top phase where it is removed from the mixture and purified. The hydrophilic ionic liquid is recycled to lyse new microalgae suspensions.

METHOD OF SEPARATING URANIUM FROM ALLOYS

DOEpatents

Chiotti, P.; Shoemaker, H.E.

1960-06-28

Uranium can be recovered from metallic uraniumthorium mixtures containing uranium in comparatively small amounts. The method of recovery comprises adding a quantity of magnesium to a mass to obtain a content of from 48 to 85% by weight; melting and forming a magnesium-thorium alloy at a temperature of between 585 and 800 deg C; agitating the mixture, allowing the mixture to settle whereby two phases, a thorium-containing magnesium-rich liquid phase and a solid uranium-rich phase, are formed; and separating the two phases.

Ion chromatography with the indirect ultraviolet detection of alkali metal ions and ammonium using imidazolium ionic liquid as ultraviolet absorption reagent and eluent.

PubMed

Liu, Yong-Qiang; Yu, Hong

2016-08-01

Indirect ultraviolet detection was conducted in ultraviolet-absorption-agent-added mobile phase to complete the detection of the absence of ultraviolet absorption functional group in analytes. Compared with precolumn derivatization or postcolumn derivatization, this method can be widely used, has the advantages of simple operation and good linear relationship. Chromatographic separation of Li(+) , Na(+) , K(+) , and NH4 (+) was performed on a carboxylic acid base cation exchange column using imidazolium ionic liquid/acid/organic solvent as the mobile phase, in which imidazolium ionic liquids acted as ultraviolet absorption reagent and eluting agent. The retention behaviors of four kinds of cations are discussed, and the mechanism of separation and detection are described. The main factors influencing the separation and detection were the background ultraviolet absorption reagent and the concentration of hydrogen ion in the ion chromatography-indirect ultraviolet detection. The successful separation and detection of Li(+) , Na(+) , K(+) , and NH4 (+) within 13 min was achieved using the selected chromatographic conditions, and the detection limits (S/N = 3) were 0.02, 0.11, 0.30, and 0.06 mg/L, respectively. A new separation and analysis method of alkali metal ions and ammonium by ion chromatography with indirect ultraviolet detection method was developed, and the application range of ionic liquid was expanded. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Anomalous partitioning of water in coexisting liquid phases of lipid multilayers near 100% relative humidity

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

Ma, Yicong; Ghosh, Sajal K.; Bera, Sambhunath

2015-11-30

X-ray diffraction is used to determine the hydration dependence of a ternary mixture lipid multilayer structure which has phase separated into liquid-ordered (Lo) and liquid-disordered (Ld) phases. An anomaly is observed in the swelling behavior of the Ld phase at a relative humidity (RH) close to 100%, which is different from the anomalous swelling happens close to the main lipid gel-fluid transition. The lamellar repeat distance of the Ld phase swells by an extra 4 Å, well beyond the equilibrium spacing predicted by the inter-bilayer forces. This anomalous swelling is caused by the hydrophobic mismatch energy at the domain boundaries,more » which produces surprisingly long range effect.« less

Evaluation of the slurry management strategy and the integration of the composting technology in a pig farm - Agronomical and environmental implications.

PubMed

Sáez, José A; Clemente, Rafael; Bustamante, M Ángeles; Yañez, David; Bernal, M Pilar

2017-05-01

The changes in livestock production systems towards intensification frequently lead to an excess of manure generation with respect to the agricultural land available for its soil application. However, treatment technologies can help in the management of manures, especially in N-surplus areas. An integrated slurry treatment system based on solid-liquid separation, aerobic treatment of the liquid and composting the solid fraction was evaluated in a pig farm (sows and piglets) in the South of Spain. Solid fraction separation using a filter band connected to a screw press had low efficiency (38%), which was greatly improved incorporating a rotatory sieve (61%). The depuration system was very efficient for the liquid, with total removal of 84% total solids, 87% volatile solids, and 98% phosphorus. Two composting systems were tested through mechanical turning of: 1- a mixture of solid fraction stored for 1 month after solid-liquid separation and cereal straw; 2- recently-separated solid fraction mixed with cotton gin waste. System 2 was recommended for the farm, as it exhibited a fast temperature rise and a long thermophilic phase to ensure compost sanitisation, and high recovery of nutrients (TN 77%, P and K > 85%) and organic matter (45%). The composts obtained were mature, stable and showed a high degree of humification of their organic matter, absence of phytotoxicity and concentrations of nutrients similar to other composts from pig manure or separated slurry solids. However, the introduction of slurry from piglets into the solid-liquid separation system should be avoided in order to reduce the content of Zn in the compost, which lowers its quality. The slurry separation followed by composting of the solid fraction using a passive windrow system, and aeration of the liquid phase, was the most recommendable procedure for the reduction of GHG emissions on the farm. Copyright © 2017 Elsevier Ltd. All rights reserved.

Evaluation of target efficiencies for solid-liquid separation steps in biofuels production.

PubMed

Kochergin, Vadim; Miller, Keith

2011-01-01

Development of liquid biofuels has entered a new phase of large scale pilot demonstration. A number of plants that are in operation or under construction face the task of addressing the engineering challenges of creating a viable plant design, scaling up and optimizing various unit operations. It is well-known that separation technologies account for 50-70% of both capital and operating cost. Additionally, reduction of environmental impact creates technological challenges that increase project cost without adding to the bottom line. Different technologies vary in terms of selection of unit operations; however, solid-liquid separations are likely to be a major contributor to the overall project cost. Despite the differences in pretreatment approaches, similar challenges arise for solid-liquid separation unit operations. A typical process for ethanol production from biomass includes several solid-liquid separation steps, depending on which particular stream is targeted for downstream processing. The nature of biomass-derived materials makes it either difficult or uneconomical to accomplish complete separation in a single step. Therefore, setting realistic efficiency targets for solid-liquid separations is an important task that influences overall process recovery and economics. Experimental data will be presented showing typical characteristics for pretreated cane bagasse at various stages of processing into cellulosic ethanol. Results of generic material balance calculations will be presented to illustrate the influence of separation target efficiencies on overall process recoveries and characteristics of waste streams.

The potential of organic (electrospray- and atmospheric pressure chemical ionisation) mass spectrometric techniques coupled to liquid-phase separation for speciation analysis.

PubMed

Rosenberg, Erwin

2003-06-06

The use of mass spectrometry based on atmospheric pressure ionisation techniques (atmospheric pressure chemical ionisation, APCI, and electrospray ionisation, ESI) for speciation analysis is reviewed with emphasis on the literature published in and after 1999. This report accounts for the increasing interest that atmospheric pressure ionisation techniques, and in particular ESI, have found in the past years for qualitative and quantitative speciation analysis. In contrast to element-selective detectors, organic mass spectrometric techniques provide information on the intact metal species which can be used for the identification of unknown species (particularly with MS-MS detection) or the confirmation of the actual presence of species in a given sample. Due to the complexity of real samples, it is inevitable in all but the simplest cases to couple atmospheric pressure MS detection to a separation technique. Separation in the liquid phase (capillary electrophoresis or liquid chromatography in reversed phase, ion chromatographic or size-exclusion mode) is particularly suitable since the available techniques cover a very wide range of analyte polarities and molecular mass. Moreover, derivatisation can normally be avoided in liquid-phase separation. Particularly in complex environmental or biological samples, separation in one dimension is not sufficient for obtaining adequate resolution for all relevant species. In this case, multi-dimensional separation, based on orthogonal separation techniques, has proven successful. ESI-MS is also often used in parallel with inductively coupled plasma MS detection. This review is structured in two parts. In the first, the fundamentals of atmospheric pressure ionisation techniques are briefly reviewed. The second part of the review discusses recent applications including redox species, use of ESI-MS for structural elucidation of metal complexes, characterisation and quantification of small organometallic species with relevance to environment, health and food. Particular attention is given to the characterisation of biomolecules and metalloproteins (metallothioneins and phytochelatins) and to the investigation of the interaction of metals and biomolecules. Particularly in the latter field, ESI-MS is the ideal technique due to the softness of the ionisation process which allows to assume that the detected gas-phase ions are a true representation of the ions or ion-biomolecule complexes prevalent in solution. It is particularly this field, important to biochemistry, physiology and medical chemistry, where we can expect significant developments also in the future.

Selective ionic liquid ferrofluid based dispersive-solid phase extraction for simultaneous preconcentration/separation of lead and cadmium in milk and biological samples.

PubMed

Fasih Ramandi, Negin; Shemirani, Farzaneh

2015-01-01

For the first time, a selective ionic liquid ferrofluid has been used in dispersive solid phase extraction (IL-FF-D-SPE) for simultaneous preconcentration and separation of lead and cadmium in milk and biological samples combined with flame atomic absorption spectrometry. To improve the selectivity of the ionic liquid ferrofluid, the surface of TiO2 nanoparticles with a magnetic core as sorbent was modified by loading 1-(2-pyridylazo)-2-naphtol. Due to the rapid injection of an appropriate amount of ionic liquid ferrofluid into the aqueous sample by a syringe, extraction can be achieved within a few seconds. In addition, based on the attraction of the ionic liquid ferrofluid to a magnet, no centrifugation step is needed for phase separation. The experimental parameters of IL-FF-D-SPE were optimized using a Box-Behnken design (BBD) after a Plackett-Burman screening design. Under the optimum conditions, the relative standard deviations of 2.2% and 2.4% were obtained for lead and cadmium, respectively (n=7). The limit of detections were 1.21 µg L(-1) for Pb(II) and 0.21 µg L(-1) for Cd(II). The preconcentration factors were 250 for lead and 200 for cadmium and the maximum adsorption capacities of the sorbent were 11.18 and 9.34 mg g(-1) for lead and cadmium, respectively. Copyright © 2014 Elsevier B.V. All rights reserved.

Stationary-phase optimized selectivity liquid chromatography: development of a linear gradient prediction algorithm.

PubMed

De Beer, Maarten; Lynen, Fréderic; Chen, Kai; Ferguson, Paul; Hanna-Brown, Melissa; Sandra, Pat

2010-03-01

Stationary-phase optimized selectivity liquid chromatography (SOS-LC) is a tool in reversed-phase LC (RP-LC) to optimize the selectivity for a given separation by combining stationary phases in a multisegment column. The presently (commercially) available SOS-LC optimization procedure and algorithm are only applicable to isocratic analyses. Step gradient SOS-LC has been developed, but this is still not very elegant for the analysis of complex mixtures composed of components covering a broad hydrophobicity range. A linear gradient prediction algorithm has been developed allowing one to apply SOS-LC as a generic RP-LC optimization method. The algorithm allows operation in isocratic, stepwise, and linear gradient run modes. The features of SOS-LC in the linear gradient mode are demonstrated by means of a mixture of 13 steroids, whereby baseline separation is predicted and experimentally demonstrated.

Gradient stationary phase optimized selectivity liquid chromatography with conventional columns.

PubMed

Chen, Kai; Lynen, Frédéric; Szucs, Roman; Hanna-Brown, Melissa; Sandra, Pat

2013-05-21

Stationary phase optimized selectivity liquid chromatography (SOSLC) is a promising technique to optimize the selectivity of a given separation. By combination of different stationary phases, SOSLC offers excellent possibilities for method development under both isocratic and gradient conditions. The so far available commercial SOSLC protocol utilizes dedicated column cartridges and corresponding cartridge holders to build up the combined column of different stationary phases. The present work is aimed at developing and extending the gradient SOSLC approach towards coupling conventional columns. Generic tubing was used to connect short commercially available LC columns. Fast and base-line separation of a mixture of 12 compounds containing phenones, benzoic acids and hydroxybenzoates under both isocratic and linear gradient conditions was selected to demonstrate the potential of SOSLC. The influence of the connecting tubing on the deviation of predictions is also discussed.

Phase-field modeling of liquids splitting between separating surfaces and its application to high-resolution roll-based printing technologies

NASA Astrophysics Data System (ADS)

Hizir, F. E.; Hardt, D. E.

2017-05-01

An in-depth understanding of the liquid transport in roll-based printing systems is essential for advancing the roll-based printing technology and enhancing the performance of the printed products. In this study, phase-field simulations are performed to characterize the liquid transport in roll-based printing systems, and the phase-field method is shown to be an effective tool to simulate the liquid transport. In the phase-field simulations, the liquid transport through the ink transfer rollers is approximated as the stretching and splitting of liquid bridges with pinned or moving contact lines between vertically separating surfaces. First, the effect of the phase-field parameters and the mesh characteristics on the simulation results is examined. The simulation results show that a sharp interface limit is approached as the capillary width decreases while keeping the mobility proportional to the capillary width squared. Close to the sharp interface limit, the mobility changes over a specified range are observed to have no significant influence on the simulation results. Next, the ink transfer from the cells on the surface of an ink-metering roller to the surface of stamp features is simulated. Under negligible inertial effects and in the absence of gravity, the amount of liquid ink transferred from an axisymmetric cell with low surface wettability to a stamp with high surface wettability is found to increase as the cell sidewall steepness and the cell surface wettability decrease and the stamp surface wettability and the capillary number increase. Strategies for improving the resolution and quality of roll-based printing are derived based on an analysis of the simulation results. The application of novel materials that contain cells with irregular surface topography to stamp inking in high-resolution roll-based printing is assessed.

Separation of cucurbitane triterpenoids from bitter melon drinks and determination of partition coefficients using vortex-assisted dispersive liquid-phase microextraction followed by UHPLC analysis

USDA-ARS?s Scientific Manuscript database

A rapid, effective technique applying vortex-assisted liquid–liquid microextraction (VALLME) prior to ultra high performance liquid chromatography-evaporating light scattering detectection/ mass spectroscopy (UHPLC-ELSD/MS) determination was developed for the analysis of four cucurbitane triterpenoi...

Study of liquid?liquid demixing from drug solution

NASA Astrophysics Data System (ADS)

Lafferrère, Laurent; Hoff, Christian; Veesler, Stéphane

2004-09-01

In pharmaceutical industry, a deep understanding of the phase diagram is required in design of crystallization processes. We have investigated the phase diagram of a pharmaceutical compound (C 35H 41Cl 2N 3O 2) in a mixture of ethanol/water. This phase diagram exhibits a solid-solid (polymorphism) and a liquid-liquid-phase separation (LLPS) as a function of temperature and drug substance concentration. This study focuses on the LLPS which is metastable with respect to the crystallization of the two polymorphs FI and FII of C 35H 41Cl 2N 3O 2 in an ethanol/water mixture. The LLPS is metastable towards the solubility curve on the whole solvent-solute concentrations and temperature range studied. The LLPS occurred within the metastable zone for crystallization. In our experiments the liquid-liquid-phase transition prevented the drug from crystallizing, while it changed the medium and the conditions of crystallization, which consequently affected the process. The coexistence curves for the liquid phases, also named TL-L boundary, and the spinodal line were measured for a ternary mixture of water-drug-ethanol at atmospheric pressure over a temperature range of 10-50°C. This temperature range corresponds to that used in the crystallization process. Static Light Scattering, HPLC measurements and Karl-Fischer titration were applied to investigate the drug-phase diagram. The isoplethe section of the phase diagram exhibits four regions: one homogeneous (one liquid) and three two-phases (two regions with one liquid+one solid and one region with two liquids), the two solids phases being two polymorphs.

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.

Confinement-Driven Phase Separation of Quantum Liquid Mixtures

NASA Astrophysics Data System (ADS)

Prisk, T. R.; Pantalei, C.; Kaiser, H.; Sokol, P. E.

2012-08-01

We report small-angle neutron scattering studies of liquid helium mixtures confined in Mobil Crystalline Material-41 (MCM-41), a porous silica glass with narrow cylindrical nanopores (d=3.4nm). MCM-41 is an ideal model adsorbent for fundamental studies of gas sorption in porous media because its monodisperse pores are arranged in a 2D triangular lattice. The small-angle scattering consists of a series of diffraction peaks whose intensities are determined by how the imbibed liquid fills the pores. Pure He4 adsorbed in the pores show classic, layer-by-layer film growth as a function of pore filling, leaving the long range symmetry of the system intact. In contrast, the adsorption of He3-He4 mixtures produces a structure incommensurate with the pore lattice. Neither capillary condensation nor preferential adsorption of one helium isotope to the pore walls can provide the symmetry-breaking mechanism. The scattering is consistent with the formation of randomly distributed liquid-liquid microdomains ˜2.3nm in size, providing evidence that confinement in a nanometer scale capillary can drive local phase separation in quantum liquid mixtures.

Fast, simple and efficient salting-out assisted liquid-liquid extraction of naringenin from fruit juice samples prior to their enantioselective determination by liquid chromatography.

PubMed

Magiera, Sylwia; Kwietniowska, Ewelina

2016-11-15

In this study, an easy, simple and efficient method for the determination of naringenin enantiomers in fruit juices after salting-out-assisted liquid-liquid extraction (SALLE) and high-performance liquid chromatography (HPLC) with diode-array detection (DAD) was developed. The sample treatment is based on the use of water-miscible acetonitrile as the extractant and acetonitrile phase separation under high-salt conditions. After extraction, juice samples were incubated with hydrochloric acid in order to achieve hydrolysis of naringin to naringenin. The hydrolysis parameters were optimized by using a half-fraction factorial central composite design (CCD). After sample preparation, chromatographic separation was obtained on a Chiralcel® OJ-RH column using the mobile phase consisting of 10mM aqueous ammonium acetate:methanol:acetonitrile (50:30:20; v/v/v) with detection at 288nm. The average recovery of the analyzed compounds ranged from 85.6 to 97.1%. The proposed method was satisfactorily used for the determination of naringenin enantiomers in various fruit juices samples. Copyright © 2016 Elsevier Ltd. All rights reserved.

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.

Systematic Comparison of Reverse Phase and Hydrophilic Interaction Liquid Chromatography Platforms for the Analysis of N-linked Glycans

PubMed Central

Walker, S. Hunter; Carlisle, Brandon C.; Muddiman, David C.

2013-01-01

Due to the hydrophilic nature of glycans, reverse phase chromatography has not been widely used as a glycomic separation technique coupled to mass spectrometry. Other approaches such as hydrophilic interaction chromatography and porous graphitized carbon chromatography are often employed, though these strategies frequently suffer from decreased chromatographic resolution, long equilibration times, indefinite retention, and column bleed. Herein, it is shown that through an efficient hydrazone formation derivatization of N-linked glycans (∼4 hr of additional sample preparation time which is carried out in parallel), numerous experimental and practical advantages are gained when analyzing the glycans by online reverse phase chromatography. These benefits include an increased number of glycans detected, increased peak capacity of the separation, and the ability to analyze glycans on the identical liquid chromatography-mass spectrometry platform commonly used for proteomic analyses. The data presented show that separation of derivatized N-linked glycans by reverse phase chromatography significantly out-performs traditional separation of native or derivatized glycans by hydrophilic interaction chromatography. Furthermore, the movement to a more ubiquitous separation technique will afford numerous research groups the opportunity to analyze both proteomic and glycomic samples on the same platform with minimal time and physical change between experiments, increasing the efficiency of ‘multi-omic’ biological approaches. PMID:22954204

Naturally occurring reverse tilt domains in a high-pretilt alignment nematic liquid crystal

NASA Astrophysics Data System (ADS)

Wang, Ruiting; Atherton, Timothy J.; Zhu, Minhua; Petschek, Rolfe G.; Rosenblatt, Charles

2007-08-01

A cell whose substrates were coated with the polyamic acid SE1211 (Nissan Chemical Industries) and baked at high temperatures was filled with a nematic liquid crystal in the isotropic phase. On cooling into the nematic phase, naturally occurring and temporally and thermally robust reverse tilt domains separated by thin filamentlike walls were observed. The properties of these structures are reported.

REMOVAL OF CERTAIN FISSION PRODUCT METALS FROM LIQUID BISMUTH COMPOSITIONS

DOEpatents

Dwyer, O.E.; Howe, H.E.; Avrutik, E.R.

1959-11-24

A method is described for purifying a solution of urarium in liquid bismuth containing at least one metal from the group consisting of selenium, tellurium, palladium, ruthenium, rhodium, niobium, and zirconium. The solution is contacted with zinc in an inert atmosphere to form a homogeneous melt, a solid zinc phase is formed, and the zinc phase containing the metal is separated from the melt.

Shearing of nanoscopic bridges in two-component thin liquid layers between chemically patterned walls.

PubMed

Hemming, C J; Patey, G N

2004-10-01

Bridge phases associated with a phase transition between two liquid phases occur when a two-component liquid mixture is confined between chemically patterned walls. In the bulk the liquid mixture with components A, B undergoes phase separation into an A-rich phase and a B-rich phase. The walls bear stripes attractive to A. In the bridge phase A-rich and B-rich regions alternate. Grand canonical Monte Carlo studies are performed with the alignment between stripes on opposite walls varied. Misalignment of the stripes places the nanoscopic liquid bridges under shear strain. The bridges exert a Hookean restoring force on the walls for small displacements from equilibrium. As the strain increases there are deviations from Hooke's law. Eventually there is an abrupt yielding of the bridges. Molecular dynamics simulations show the bridges form or disintegrate on time scales which are fast compared to wall motion and transport of molecules into or from the confined space. Some interesting possible applications of the phenomena are discussed. (c) 2004 American Institute of Physics

Development of tropine-salt aqueous two-phase systems and removal of hydrophilic ionic liquids from aqueous solution.

PubMed

Wu, Haoran; Yao, Shun; Qian, Guofei; Song, Hang

2016-08-26

A novel aqueous two-phase systems (ATPS) composed of a small molecule organic compound tropine and an organic or inorganic salt aqueous solution has been developed for the first time. The phase behavior of tropine-salt ATPS was systemically investigated and the phase equilibrium data were measured in different temperatures and concentrations and correlated by the Merchuk equation with satisfactory results. The detection of the conductivity and particle size proved the formation of micelle in the process of forming tropine-salt ATPS. The separation application of the ATPS was assessed with the removal of hydrophilic benzothiazolium-based ionic liquids (ILs) from aqueous solution. The result showed that ILs were effectively extracted into the top tropine-rich phase. Finally, ILs in the top tropine-rich phase were further separated by the means of adsorption-desorption with DM301 macroporous resin and ethanol. The method of novel tropine-salt ATPS combined with adsorption-desorption is demonstrated a promising alternative thought and approach for the removal or recovery of hydrophilic compounds from aqueous media and also could provide a potential application for bio-separation. Copyright © 2016. Published by Elsevier B.V.

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.

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.

Revisiting resolution in hydrodynamic countercurrent chromatography: tubing bore effect.

PubMed

Berthod, A; Faure, K

2015-04-17

A major challenge in countercurrent chromatography (CCC), the technique that works with a support-free biphasic liquid system, is to retain the liquid stationary phase inside the CCC column (Sf parameter). Two solutions are commercially available: the hydrostatic CCC columns, also called centrifugal partition chromatographs (CPC), with disks of interconnected channels and rotary seals, and the hydrodynamic CCC columns with bobbins of coiled open tube and no rotary seals. It was demonstrated that the amount of liquid stationary phase retained by a coiled tube was higher with larger bore tubing than with small bore tubes. At constant column volume, small bore tubing will be longer producing more efficiency than larger bore tube that will better retain the liquid stationary phase. Since the resolution equation in CCC is depending on both column efficiency and stationary phase retention ratio, the influence of the tubing bore should be studied. This theoretical work showed that there is an optimum tubing bore size depending on solute partition coefficient and mobile phase flow rate. The interesting result of the theoretical study is that larger tubing bores allow for dramatically reduced experiment durations for all solutes: in reversed phase CCC (polar mobile phase), hydrophobic solutes are usually highly retained. These apolar solutes can be separated by the same coil at high flow rates and reduced Sf with similar retention times as polar solutes separated at smaller flow rates and much higher Sf. Copyright © 2015 Elsevier B.V. All rights reserved.

Chiral ligand exchange high-speed countercurrent chromatography: mechanism, application and comparison with conventional liquid chromatography in enantioseparation of aromatic α-hydroxyl acids

PubMed Central

Tong, Shengqiang; Shen, Mangmang; Cheng, Dongping; Ito, Yoichiro; Yan, Jizhong

2014-01-01

This work concentrates on the separation mechanism and application of chiral ligand exchange high-speed countercurrent chromatography (HSCCC) in enantioseparations, and comparison with traditional chiral ligand exchange high performance liquid chromatography (HPLC). The enantioseparation of ten aromatic α-hydroxyl acids were performed by these two chromatographic methods. Results showed that five of the racemates were successfully enantioseparated by HSCCC while only three of the racemates could be enantioseparated by HPLC using a suitable chiral ligand mobile phase additive. For HSCCC, the two-phase solvent system was composed of butanol-water (1:1, v/v), to which N-n-dodecyl-L-proline was added in the organic phase as chiral ligand and cupric acetate was added in the aqueous phase as a transition metal ion. Various operation parameters in HSCCC were optimized by enantioselective liquid-liquid extraction. Based on the results of the present studies the separation mechanism for HSCCC was proposed. For HPLC, the optimized mobile phase composed of aqueous solution containing 6 mmol L−1 L-phenylalanine and 3 mmol L−1 cupric sulfate and methanol was used for enantioseparation. Among three ligands tested on a conventional reverse stationary phase column, only one was found to be effective. In the present studies HSCCC presented unique advantages due to its high versatility of two-phase solvent systems and it could be used as an alternative method for enantioseparations. PMID:25087742

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.

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.

The mechanical properties of phase separated protein droplets

NASA Astrophysics Data System (ADS)

Jawerth, Louise; Ijavi, Mahdiye; Patel, Avinash; Saha, Shambaditya; Jülicher, Frank; Hyman, Anthony

In vivo, numerous proteins associate into liquid compartments by de-mixing from the surrounding solution, similar to oil molecules in water. Many of these proteins and their corresponding liquid compartments play a crucial role in important biological processes, for instance germ line specification in C. elegans or in neurodegenerative diseases such as Amyotrophic lateral sclerosis (ALS). However, despite their importance, very little is known about the physical properties of the resulting droplets as well as the physical mechanisms that control their phase separation from solution. To gain a deeper understanding of these aspects, we study a few such proteins in vitro. When these proteins are purified and added to a physiological buffer, they phase separate into droplets ranging in size from a few to tens of microns with liquid-like behavior similar to their physiological counterparts. By attaching small beads to the surface of the droplets, we can deform the droplets by manipulating the beads directly using optical tweezers. By measuring the force required to deform the droplets we determine their surface tension, elasticity and viscosity as well as the frequency response of these properties. We also measure these properties using passive micro-rheology.

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.

Isocratic non-aqueous reversed-phase high-performance liquid chromatographic separation of capsanthin and capsorubin in red peppers (Capsicum annuum L.), paprika and oleoresin.

PubMed

Weissenberg, M; Schaeffler, I; Menagem, E; Barzilai, M; Levy, A

1997-01-03

A simple, rapid high-performance liquid chromatography method has been devised in order to separate and quantify the xanthophylls capsorubin and capasanthin present in red pepper (Capsicum annuum L.) fruits and preparations made from them (paprika and oleoresin). A reversed-phase isocratic non-aqueous system allows the separation of xanthophylls within a few minutes, with detection at 450 nm, using methyl red as internal standard to locate the various carotenoids and xanthophylls found in plant extracts. The selection of extraction solvents, mild saponification conditions, and chromatographic features is evaluated and discussed. The method is proposed for rapid screening of large plant populations, plant selection, as well as for paprika products and oleoresin, and also for nutrition and quality control studies.

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

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.

Versatile ligands for high-performance liquid chromatography: An overview of ionic liquid-functionalized stationary phases.

PubMed

Zhang, Mingliang; Mallik, Abul K; Takafuji, Makoto; Ihara, Hirotaka; Qiu, Hongdeng

2015-08-05

Ionic liquids (ILs), a class of unique substances composed purely by cation and anions, are renowned for their fascinating physical and chemical properties, such as negligible volatility, high dissolution power, high thermal stability, tunable structure and miscibility. They are enjoying ever-growing applications in a great diversity of disciplines. IL-modified silica, transforming the merits of ILs into chromatographic advantages, has endowed the development of high-performance liquid chromatography (HPLC) stationary phase with considerable vitality. In the last decade, IL-functionalized silica stationary phases have evolved into a series of branches to accommodate to different HPLC modes. An up-to-date overview of IL-immobilized stationary phases is presented in this review, and divided into five parts according to application mode, i.e., ion-exchange, normal-phase, reversed-phase, hydrophilic interaction and chiral recognition. Specific attention is channeled to synthetic strategies, chromatographic behavior and separation performance of IL-functionalized silica stationary phases. Copyright © 2015 Elsevier B.V. All rights reserved.

Vapor-liquid coexistence of the Stockmayer fluid in nonuniform external fields.

PubMed

Samin, Sela; Tsori, Yoav; Holm, Christian

2013-05-01

We investigate the structure and phase behavior of the Stockmayer fluid in the presence of nonuniform electric fields using molecular simulation. We find that an initially homogeneous vapor phase undergoes a local phase separation in a nonuniform field due to the combined effect of the field gradient and the fluid vapor-liquid equilibrium. This results in a high-density fluid condensing in the strong field region. The system polarization exhibits a strong field dependence due to the fluid condensation.

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.

Observations and implications of liquid–liquid phase separation at high relative humidities in secondary organic material produced by α-pinene ozonolysis without inorganic salts

DOE PAGES

Renbaum-Wolff, Lindsay; Song, Mijung; Marcolli, Claudia; ...

2016-07-01

Particles consisting of secondary organic material (SOM) are abundant in the atmosphere. In order to predict the role of these particles in climate, visibility and atmospheric chemistry, information on particle phase state (i.e., single liquid, two liquids and solid) is needed. Our paper focuses on the phase state of SOM particles free of inorganic salts produced by the ozonolysis of α-pinene. Phase transitions were investigated in the laboratory using optical microscopy and theoretically using a thermodynamic model at 290 K and for relative humidities ranging from < 0.5 to 100%. In the laboratory studies, a single phase was observed frommore » 0 to 95% relative humidity (RH) while two liquid phases were observed above 95% RH. For increasing RH, the mechanism of liquid–liquid phase separation (LLPS) was spinodal decomposition. The RH range over which two liquid phases were observed did not depend on the direction of RH change. In the modeling studies, the SOM took up very little water and was a single organic-rich phase at low RH values. At high RH, the SOM underwent LLPS to form an organic-rich phase and a water-rich phase, consistent with the laboratory studies. The presence of LLPS at high RH values can have consequences for the cloud condensation nuclei (CCN) activity of SOM particles. In the simulated Köhler curves for SOM particles, two local maxima were observed. Depending on the composition of the SOM, the first or second maximum can determine the critical supersaturation for activation. Recently researchers have observed inconsistencies between measured CCN properties of SOM particles and hygroscopic growth measured below water saturation (i.e., hygroscopic parameters measured below water saturation were inconsistent with hygroscopic parameters measured above water saturation). Furthermore, the work presented here illustrates that such inconsistencies are expected for systems with LLPS when the water uptake at subsaturated conditions represents the hygroscopicity of an organic-rich phase while the barrier for CCN activation can be determined by the second maximum in the Köhler curve when the particles are water rich.« less

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.

Evidence of low-density and high-density liquid phases and isochore end point for water confined to carbon nanotube

PubMed Central

Nomura, Kentaro; Kaneko, Toshihiro; Bai, Jaeil; Francisco, Joseph S.; Yasuoka, Kenji; Zeng, Xiao Cheng

2017-01-01

Possible transition between two phases of supercooled liquid water, namely the low- and high-density liquid water, has been only predicted to occur below 230 K from molecular dynamics (MD) simulation. However, such a phase transition cannot be detected in the laboratory because of the so-called “no-man’s land” under deeply supercooled condition, where only crystalline ices have been observed. Here, we show MD simulation evidence that, inside an isolated carbon nanotube (CNT) with a diameter of 1.25 nm, both low- and high-density liquid water states can be detected near ambient temperature and above ambient pressure. In the temperature–pressure phase diagram, the low- and high-density liquid water phases are separated by the hexagonal ice nanotube (hINT) phase, and the melting line terminates at the isochore end point near 292 K because of the retracting melting line from 292 to 278 K. Beyond the isochore end point (292 K), low- and high-density liquid becomes indistinguishable. When the pressure is increased from 10 to 600 MPa along the 280-K isotherm, we observe that water inside the 1.25-nm-diameter CNT can undergo low-density liquid to hINT to high-density liquid reentrant first-order transitions. PMID:28373562

Separation performance of cucurbit[7]uril in ionic liquid-based sol-gel coating as stationary phase for capillary gas chromatography.

PubMed

Wang, Xiaogang; Qi, Meiling; Fu, Ruonong

2014-12-05

Here we report the separation performance of a new stationary phase of cucurbit[7]uril (CB7) incorporated into an ionic liquid-based sol-gel coating (CB7-SG) for capillary gas chromatography (GC). The CB7-SG stationary phase showed an average polarity of 455, suggesting its polar nature. Abraham system constants revealed that its major interactions with analytes include H-bond basicity (a), dipole-dipole (s) and dispersive (l) interactions. The CB7-SG stationary phase achieved baseline separation for a wide range of analytes with symmetrical peak shapes and showed advantages over the conventional polar stationary phase that failed to resolve some critical analytes. Also, it exhibited different retention behaviors from the conventional stationary phase in terms of retention times and elution order. Most interestingly, in contrast to the conventional polar phase, the CB7-SG stationary phase exhibited longer retentions for analytes of lower polarity but relatively comparable retentions for polar analytes such as alcohols and phenols. The high resolving ability and unique retention behaviors of the CB7-SG stationary phase may stem from the comprehensive interactions of the aforementioned interactions and shape selectivity. Moreover, the CB7-SG column showed good peak shapes for analytes prone to peak tailing, good thermal stability up to 280°C and separation repeatability with RSD values in the range of 0.01-0.11% for intra-day, 0.04-0.41% for inter-day and 2.5-6.0% for column-to-column, respectively. As demonstrated, the proposed coating method can simultaneously address the solubility problem with CBs for the intended purpose and achieve outstanding GC separation performance. Copyright © 2014 Elsevier B.V. All rights reserved.

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.

Fluid-sensitive nanoscale switching with quantum levitation controlled by α -Sn/β -Sn phase transition

NASA Astrophysics Data System (ADS)

Boström, Mathias; Dou, Maofeng; Malyi, Oleksandr I.; Parashar, Prachi; Parsons, Drew F.; Brevik, Iver; Persson, Clas

2018-03-01

We analyze the Lifshitz pressure between silica and tin separated by a liquid mixture of bromobenzene and chlorobenzene. We show that the phase transition from semimetallic α -Sn to metallic β -Sn can switch Lifshitz forces from repulsive to attractive. This effect is caused by the difference in dielectric functions of α -Sn and β -Sn , giving both attractive and repulsive contributions to the total Lifshitz pressure in different frequency regions controlled by the composition of the intervening liquid mixture. In this way, one may be able to produce phase-transition-controlled quantum levitation in a liquid medium.

Supercooling of aqueous dimethylsulfoxide solution at normal and high pressures: Evidence for the coexistence of phase-separated aqueous dimethylsulfoxide solutions of different water structures.

PubMed

Kanno, H; Kajiwara, K; Miyata, K

2010-05-21

Supercooling behavior of aqueous dimethylsulfoxide (DMSO) solution was investigated as a function of DMSO concentration and at high pressures. A linear relationship was observed for T(H) (homogeneous ice nucleation temperature) and T(m) (melting temperature) for the supercooling of aqueous DMSO solution at normal pressure. Analysis of the DTA (differential thermal analysis) traces for homogeneous ice crystallization in the bottom region of the T(H) curve for a DMSO solution of R=20 (R: moles of water/moles of DMSO) at high pressures supported the contention that the second critical point (SCP) of liquid water should exist at P(c2)= approximately 200 MPa and at T(c2)<-100 degrees C (P(c2): pressure of SCP, T(c2): temperature of SCP). The presence of two T(H) peaks for DMSO solutions (R=15, 12, and 10) suggests that phase separation occurs in aqueous DMSO solution (R

Supercooling of aqueous dimethylsulfoxide solution at normal and high pressures: Evidence for the coexistence of phase-separated aqueous dimethylsulfoxide solutions of different water structures

NASA Astrophysics Data System (ADS)

Kanno, H.; Kajiwara, K.; Miyata, K.

2010-05-01

Supercooling behavior of aqueous dimethylsulfoxide (DMSO) solution was investigated as a function of DMSO concentration and at high pressures. A linear relationship was observed for TH (homogeneous ice nucleation temperature) and Tm (melting temperature) for the supercooling of aqueous DMSO solution at normal pressure. Analysis of the DTA (differential thermal analysis) traces for homogeneous ice crystallization in the bottom region of the TH curve for a DMSO solution of R =20 (R: moles of water/moles of DMSO) at high pressures supported the contention that the second critical point (SCP) of liquid water should exist at Pc2=˜200 MPa and at Tc2<-100 °C (Pc2: pressure of SCP, Tc2: temperature of SCP). The presence of two TH peaks for DMSO solutions (R =15, 12, and 10) suggests that phase separation occurs in aqueous DMSO solution (R ≤15) at high pressures and low temperatures (<-90 °C). The pressure dependence of the two TH curves for DMSO solutions of R =10 and 12 indicates that the two phase-separated components in the DMSO solution of R =10 have different liquid water structures [LDL-like and HDL-like structures (LDL: low-density liquid water, HDL: high-density liquid water)] in the pressure range of 120-230 MPa.

Development and evaluation of a hydrophilic interaction liquid chromatography-MS/MS method to quantify 19 nucleobases and nucleosides in rat plasma.

PubMed

Du, Yan; Li, Yin-Jie; Hu, Xun-Xiu; Deng, Xu; Qian, Zeng-Ting; Li, Zheng; Guo, Meng-Zhe; Tang, Dao-Quan

2017-04-01

As essential endogenous compounds, nucleobases and nucleosides fulfill various functions in living organisms. This study presents the development and validation of a new hydrophilic interaction liquid chromatography tandem mass spectrometry method for simultaneous quantification of 19 nucleobases and nucleosides in rat plasma. For the sample preparation, 15 kinds of protein precipitants were evaluated according to the chromatographic profile and ion response of analytes. The optimization of chromatographic separation was respectively performed using reversed-phase liquid chromatography and hydrophilic interaction liquid chromatography mode; each separation mode included two test columns with different stationary phases. The chromatographic profile and parameters such as half-width (W 1/2 ), capacity factor (K') and tailing factor (f t ) were used to evaluate the separation efficiencies. Furthermore, the adopted composition of two mobile phase systems and the concentrations of the additives in the optimum buffer system were also investigated. The developed method was fully validated and successfully applied quantitatively to determine 19 nucleobases and nucleosides in plasma from normal and diabetic nephropathy (DN) rats. Significant differences between normal and DN rats were found in plasma levels of cytosine, xanthine, thymidine, adenosine, guanosine, inosine and 8-hydroxy-2'-deoxyguanosine. This information may provide a useful reference for the discovery of potential biomarkers of DN. Copyright © 2016 John Wiley & Sons, Ltd.

Use of limonene in countercurrent chromatography: a green alkane substitute.

PubMed

Faure, Karine; Bouju, Elodie; Suchet, Pauline; Berthod, Alain

2013-05-07

Counter-current chromatography (CCC) is a preparative separation technique working with the two liquid phases of a biphasic liquid system. One phase is used as the mobile phase when the other, the stationary phase, is held in place by centrifugal fields. Limonene is a biorenewable cycloterpene solvent coming from orange peel waste. It was evaluated as a possible substitute for heptane in CCC separations. The limonene/methanol/water and heptane/methanol/water phase diagrams are very similar at room temperature. The double bonds of the limonene molecule allows for possible π-π interactions with solutes rendering limonene slightly more polar than heptane giving small differences in solute partition coefficients in the two systems. The 24% higher limonene density is a difference with heptane that has major consequences in CCC. The polar and apolar phases of the limonene/methanol/water 10/9/1 v/v have -0.025 g/cm(3) density difference (lower limonene phase) compared to +0.132 g/cm(3) with heptane (upper heptane phase). This precludes the use of this limonene system with hydrodynamic CCC columns that need significant density difference to retain a liquid stationary phase. It is an advantage with hydrostatic CCC columns because density difference is related to the working pressure drop: limonene allows one to work with high centrifugal fields and moderate pressure drop. Limonene has the capability to be a "green" alternative to petroleum-based solvents in CCC applications.

Process for analyzing CO.sub.2 in seawater

DOEpatents

Atwater, James E.; Akse, James R.; DeHart, Jeffrey

1997-01-01

The process of this invention comprises providing a membrane for separating CO.sub.2 into a first CO.sub.2 sample phase and a second CO.sub.2 analyte phase. CO.sub.2 is then transported through the membrane thereby separating the CO.sub.2 with the membrane into a first CO.sub.2 sample phase and a second CO.sub.2 analyte liquid phase including an ionized, conductive, dissociated CO.sub.2 species. Next, the concentration of the ionized, conductive, dissociated CO.sub.2 species in the second CO.sub.2 analyte liquid phase is chemically amplified using a water-soluble chemical reagent which reversibly reacts with undissociated CO.sub.2 to produce conductivity changes therein corresponding to fluctuations in the partial pressure of CO.sub.2 in the first CO.sub.2 sample phase. Finally, the chemically amplified, ionized, conductive, dissociated CO.sub.2 species is introduced to a conductivity measuring instrument. Conductivity changes in the chemically amplified, ionized, conductive, dissociated CO.sub.2 species are detected using the conductivity measuring instrument.

Laser capillary spectrophotometric acquisition of bivariate drop size and concentration data for liquid-liquid dispersion

DOEpatents

Tavlarides, L.L.; Bae, J.H.

1991-12-24

A laser capillary spectrophotometric technique measures real time or near real time bivariate drop size and concentration distribution for a reactive liquid-liquid dispersion system. The dispersion is drawn into a precision-bore glass capillary and an appropriate light source is used to distinguish the aqueous phase from slugs of the organic phase at two points along the capillary whose separation is precisely known. The suction velocity is measured, as is the length of each slug from which the drop free diameter is calculated. For each drop, the absorptivity at a given wavelength is related to the molar concentration of a solute of interest, and the concentration of given drops of the organic phase is derived from pulse heights of the detected light. This technique permits on-line monitoring and control of liquid-liquid dispersion processes. 17 figures.

Effect of polyethylene glycol on the liquid–liquid phase transition in aqueous protein solutions

PubMed Central

Annunziata, Onofrio; Asherie, Neer; Lomakin, Aleksey; Pande, Jayanti; Ogun, Olutayo; Benedek, George B.

2002-01-01

We have studied the effect of polyethylene glycol (PEG) on the liquid–liquid phase separation (LLPS) of aqueous solutions of bovine γD-crystallin (γD), a protein in the eye lens. We observe that the phase separation temperature increases with both PEG concentration and PEG molecular weight. PEG partitioning, which is the difference between the PEG concentration in the two coexisting phases, has been measured experimentally and observed to increase with PEG molecular weight. The measurements of both LLPS temperature and PEG partitioning in the ternary γD-PEG-water systems are used to successfully predict the location of the liquid–liquid phase boundary of the binary γD-water system. We show that our LLPS measurements can be also used to estimate the protein solubility as a function of the concentration of crystallizing agents. Moreover, the slope of the tie-lines and the dependence of LLPS temperature on polymer concentration provide a powerful and sensitive check of the validity of excluded volume models. Finally, we show that the increase of the LLPS temperature with PEG concentration is due to attractive protein–protein interactions. PMID:12391331

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.

Chiral stationary phase optimized selectivity liquid chromatography: A strategy for the separation of chiral isomers.

PubMed

Hegade, Ravindra Suryakant; De Beer, Maarten; Lynen, Frederic

2017-09-15

Chiral Stationary-Phase Optimized Selectivity Liquid Chromatography (SOSLC) is proposed as a tool to optimally separate mixtures of enantiomers on a set of commercially available coupled chiral columns. This approach allows for the prediction of the separation profiles on any possible combination of the chiral stationary phases based on a limited number of preliminary analyses, followed by automated selection of the optimal column combination. Both the isocratic and gradient SOSLC approach were implemented for prediction of the retention times for a mixture of 4 chiral pairs on all possible combinations of the 5 commercial chiral columns. Predictions in isocratic and gradient mode were performed with a commercially available and with an in-house developed Microsoft visual basic algorithm, respectively. Optimal predictions in the isocratic mode required the coupling of 4 columns whereby relative deviations between the predicted and experimental retention times ranged between 2 and 7%. Gradient predictions led to the coupling of 3 chiral columns allowing baseline separation of all solutes, whereby differences between predictions and experiments ranged between 0 and 12%. The methodology is a novel tool allowing optimizing the separation of mixtures of optical isomers. Copyright © 2017 Elsevier B.V. All rights reserved.

Continuous, high-flux and efficient oil/water separation assisted by an integrated system with opposite wettability

NASA Astrophysics Data System (ADS)

Li, Jian; Long, Yifei; Xu, Changcheng; Tian, Haifeng; Wu, Yanxia; Zha, Fei

2018-03-01

To resolve the drawbacks that single-mesh involved for oil/water separation, such as batch processing mode, only one phase was purified and the quick decrease in flux et al., herein, a two-way separation T-tube device was designed by integrating a pair of meshes with opposite wettability, i.e., underwater superoleophobic and superhydrophobic/superoleophilic properties. Such integrated system can continuously separate both oil and water phase from the oil/water mixtures simultaneously through one-step procedure with high flux (above 3.675 L m-2 s-1) and high separation efficiency larger than 99.8% regardless of the heavy oil or light oil involved in the mixture. Moreover, the as-prepared two meshes still maintained high separation efficiency larger than above 98.9% even after 50 cycle-usages. It worthy mentioned that this two-way separation mode essentially solves the oil liquid accumulation problem that is the single separation membrane needs to tolerate a large hydrostatic pressure caused by the accumulated liquid. We deeply believe this two-way separation system would provide a new strategy for realizing practical applications in oil spill clean-up via a continuous mode.

Gas separation and bubble behavior at a woven screen

NASA Astrophysics Data System (ADS)

Conrath, Michael; Dreyer, Michael E.

Gas-liquid two phase flows are widespread and in many applications the separation of both phases is necessary. Chemical reactors, water treatment devices or gas-free delivery of liquids like propellant are only some of them. We study the performance of a woven metal screen in respect to its phase separation behavior under static and dynamic conditions. Beside hydraulic screen resistance and static bubble point, our study also comprises the bubble detachment from the screen upon gas breakthrough. Since a woven screen is essentially an array of identical pores, analogies to bubble detachment from a needle can be established. While the bubble point poses an upper limit for pressurized gas at a wetted screen to preclude gas breakthrough, the necessary pressure for growing bubbles to detach from the screen pores a lower limit when breakthrough is already in progress. Based on that inside, the dynamic bubble point effects were constituted that relate to a trapped bubble at such a screen in liquid flow. A trapped is caused to break through the screen by the flow-induced pressure drop across it. Our model includes axially symmetric bubble shapes, degree of coverage of the screen and bubble pressurization due to hydraulic losses in the rest of the circuit. We have built an experiment that consists of a Dutch Twilled woven screen made of stainless steel in a vertical acrylic glass tube. The liquid is silicon oil SF0.65. The screen is suspended perpendicular to the liquid flow which is forced through it at variable flow rate. Controlled injection of air from a needle allows us to examine the ability of the screen to separate gas and liquid along the former mentioned effects. We present experimental data on static bubble point and detachment pressure for breakthrough at different gas supply rates that suggest a useful criterion for reliable static bubble point measurements. Results for the dynamic bubble point are presented that include i) screen pressure drop for different trapped bubble volumes, liquid flow rates and flow-induced compression, ii) typical breakthrough of a trapped bubble at rising liquid flow rate and iii) steady gas supply in steady liquid flow. It shows that our model can explain the experimental observations. One of the interesting findings for the dynamic bubble point is that hydraulic losses in the rest of the circuit will shift the breakthrough of gas to higher liquid flow rates.

About the Shape of the Melting Line as a Possible Precursor of a Liquid-Liquid Phase Transition

NASA Astrophysics Data System (ADS)

Imre, Attila R.; Rzoska, Sylwester J.

Several simple, non-mesogenic liquids can exists in two or more different liquid forms. When the liquid-liquid line, separating two liquid forms, meets the melting line, one can expect some kind of break on the melting line, caused by the different freezing/melting behaviour of the two liquid forms. Unfortunately recently several researchers are using this vein of thinking in reverse; seeing some irregularity on the melting line, they will expect a break and the appearance of a liquid-liquid line. In this short paper, we are going to show, that in the case of the high-pressure nitrogen studied recently by Mukherjee and Boehler, the high-pressure data can be easily described by a smooth, break-free function, the modified Simon-Glatzel equation. In this way, the break, suggested by them and consequently the suggested appearance of a new liquid phase of the nitrogen might be artefacts.

The morphology of blends of linear and branched polyethylenes by small-angle neutron and x-ray scattering

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

Londono, J.D.; Wignall, G.D.; Lin, J.S.

1995-12-31

The solid-state morphology and liquid-state homogeneity of blends of high-density polyethylene (HDPE) and low-density polyethylene (LDPE) were investigated by small-angle neutron and x-ray scattering (SANS and SAXS). The solid state morphology was investigated as a function of composition and cooling rate from the melt. After slow cooling, the evidence indicated that the mixtures were either completely (HDPE-rich blends) or almost completely (LDPE-rich blends) phase separated into separate HDPE and LDPE lamellae over the whole compositional range. In contrast, for rapidly quenched blends the components are extensively co-crystallized for all concentrations, though the SANS data indicated that the branched component hadmore » a tendency to be preferentially located in the inter-lamellar regions. In the liquid state, the blends were homogeneous at all compositions, showing that the solid state morphology is not determined by the melt structure, but is a function of the crystallization kinetics. Further evidence for blend homogeneity in the liquid is presented. In particular the authors examine the hypothesis that a phase separated mixture might give a scattering pattern similar to a homogeneous blend if the domain sizes were larger than the maximum spatial resolution of the SANS experiment (D > 2{pi}/Q{sub min} {approximately} 2,000 {angstrom}). In this scenario, the differential scattering cross section d{Sigma}/d{Omega}(Q) {approximately} Q{sup {minus}2}, though phase separation decreases the cross section in this Q-range with respect to the homogeneous blend. For HDPE/LDPE blends in the melt, this decrease in intensity was not observed, thus ruling out the possibility of phase separation.« less

Elucidating the weak protein-protein interaction mechanisms behind the liquid-liquid phase separation of a mAb solution by different types of additives.

PubMed

Wu, Guoliang; Wang, Shujing; Tian, Zhou; Zhang, Ning; Sheng, Han; Dai, Weiguo; Qian, Feng

2017-11-01

Liquid-liquid phase separation (LLPS) has long been observed during the physical stability investigation of therapeutic protein formulations. The buffer conditions and the presence of various excipients are thought to play important roles in the formulation development of monoclonal antibodies (mAbs). In this study, the effects of several small-molecule excipients (histidine, alanine, glycine, sodium phosphate, sodium chloride, sorbitol and sucrose) with diverse physical-chemical properties on LLPS of a model IgG1 (JM2) solutions were investigated by multiple techniques, including UV-vis spectroscopy, circular dichroism, differential scanning calorimetry/fluorimetry, size exclusion chromatography and dynamic light scattering. The LLPS of JM2 was confirmed to be a thermodynamic equilibrium process with no structural changes or irreversible aggregation of proteins. Phase diagrams of various JM2 formulations were constructed, suggesting that the phase behavior of JM2 was dependent on the solution pH, ionic strength and the presence of other excipients such as glycine, alanine, sorbitol and sucrose. Furthermore, we demonstrated that for this mAb, the interaction parameter (k D ) determined at low protein concentration appeared to be a good predictor for the occurrence of LLPS at high concentration. Copyright © 2017 Elsevier B.V. All rights reserved.

Using Environment-Sensitive Fluorescent Probes to Characterize Liquid-Liquid Phase Separation in Supersaturated Solutions of Poorly Water Soluble Compounds.

PubMed

Raina, Shweta A; Alonzo, David E; Zhang, Geoff G Z; Gao, Yi; Taylor, Lynne S

2015-11-01

Highly supersaturated aqueous solutions of poorly soluble compounds can undergo liquid-liquid phase separation (LLPS) when the concentration exceeds the "amorphous solubility". This phenomenon has been widely observed during high throughput screening of new molecular entities as well as during the dissolution of amorphous solid dispersions. In this study, we have evaluated the use of environment-sensitive fluorescence probes to investigate the formation and properties of the non-crystalline drug-rich aggregates formed in aqueous solutions as a result of LLPS. Six different environment-sensitive fluorophores were employed to study LLPS in highly supersaturated solutions of several model compounds, all dihydropyridine derivatives. Each fluoroprobe exhibited a large hypsochromic shift with decreasing environment polarity. Upon drug aggregate formation, the probes partitioned into the drug-rich phase and exhibited changes in emission wavelength and intensity consistent with sensing a lower polarity environment. The LLPS onset concentrations determined using the fluorescence measurements were in good agreement with light scattering measurements as well as theoretically estimated amorphous solubility values. Environment-sensitive fluorescence probes are useful to help understand the phase behavior of highly supersaturated aqueous solutions, which in turn is important in the context of developing enabling formulations for poorly soluble compounds.

Self-assembled cyclodextrin-modified gold nanoparticles on silica beads as stationary phase for chiral liquid chromatography and hydrophilic interaction chromatography.

PubMed

Li, Yuanyuan; Wei, Manman; Chen, Tong; Zhu, Nan; Ma, Yulong

2016-11-01

A facile strategy based on self-assembly of Au nanoparticles (AuNPs) (60±10nm in size) on the surfaces of amino-functionalized porous silica spheres under mild conditions was proposed. The resulting material possessed a core-shell structure in which AuNPs were the shell and silica spheres were the core. Then, thiolated-β-cyclodextrin (SH-β-CD) was covalently attached onto the AuNPs as chiral selector for the enantioseparation. The resultant packing material was evaluated by high-performance liquid chromatography (HPLC). The separations of nine pairs of enantiomers were achieved by using the new chiral stationary phase (CSP) in the reversed-phase liquid chromatography (RPLC) mode, respectively. The results showed the new CSP have more sufficient interaction with the analytes due to the existence of AuNPs on silica surfaces, resulting in faster mass transfer rate, compared with β-CD modified silica column. The result shed light on potential usage of chemical modified NPs as chiral selector for enantioseparation based on HPLC. In addition, the new phase was also used in hydrophilic interaction liquid chromatography (HILIC) to separate polar compounds and highly hydrophilic compounds. Copyright © 2016 Elsevier B.V. All rights reserved.

Giant plasma membrane vesicles: models for understanding membrane organization.

PubMed

Levental, Kandice R; Levental, Ilya

2015-01-01

The organization of eukaryotic membranes into functional domains continues to fascinate and puzzle cell biologists and biophysicists. The lipid raft hypothesis proposes that collective lipid interactions compartmentalize the membrane into coexisting liquid domains that are central to membrane physiology. This hypothesis has proven controversial because such structures cannot be directly visualized in live cells by light microscopy. The recent observations of liquid-liquid phase separation in biological membranes are an important validation of the raft hypothesis and enable application of the experimental toolbox of membrane physics to a biologically complex phase-separated membrane. This review addresses the role of giant plasma membrane vesicles (GPMVs) in refining the raft hypothesis and expands on the application of GPMVs as an experimental model to answer some of key outstanding problems in membrane biology. Copyright © 2015 Elsevier Inc. All rights reserved.

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.

Visualizing monolayers with a water-soluble fluorophore to quantify adsorption, desorption, and the double layer.

PubMed

Shieh, Ian C; Zasadzinski, Joseph A

2015-02-24

Contrast in confocal microscopy of phase-separated monolayers at the air-water interface can be generated by the selective adsorption of water-soluble fluorescent dyes to disordered monolayer phases. Optical sectioning minimizes the fluorescence signal from the subphase, whereas convolution of the measured point spread function with a simple box model of the interface provides quantitative assessment of the excess dye concentration associated with the monolayer. Coexisting liquid-expanded, liquid-condensed, and gas phases could be visualized due to differential dye adsorption in the liquid-expanded and gas phases. Dye preferentially adsorbed to the liquid-disordered phase during immiscible liquid-liquid phase coexistence, and the contrast persisted through the critical point as shown by characteristic circle-to-stripe shape transitions. The measured dye concentration in the disordered phase depended on the phase composition and surface pressure, and the dye was expelled from the film at the end of coexistence. The excess concentration of a cationic dye within the double layer adjacent to an anionic phospholipid monolayer was quantified as a function of subphase ionic strength, and the changes in measured excess agreed with those predicted by the mean-field Gouy-Chapman equations. This provided a rapid and noninvasive optical method of measuring the fractional dissociation of lipid headgroups and the monolayer surface potential.

Pressurized planar electrochromatography, high-performance thin-layer chromatography and high-performance liquid chromatography--comparison of performance.

PubMed

Płocharz, Paweł; Klimek-Turek, Anna; Dzido, Tadeusz H

2010-07-16

Kinetic performance, measured by plate height, of High-Performance Thin-Layer Chromatography (HPTLC), High-Performance Liquid Chromatography (HPLC) and Pressurized Planar Electrochromatography (PPEC) was compared for the systems with adsorbent of the HPTLC RP18W plate from Merck as the stationary phase and the mobile phase composed of acetonitrile and buffer solution. The HPLC column was packed with the adsorbent, which was scrapped from the chromatographic plate mentioned. An additional HPLC column was also packed with adsorbent of 5 microm particle diameter, C18 type silica based (LiChrosorb RP-18 from Merck). The dependence of plate height of both HPLC and PPEC separating systems on flow velocity of the mobile phase and on migration distance of the mobile phase in TLC system was presented applying test solute (prednisolone succinate). The highest performance, amongst systems investigated, was obtained for the PPEC system. The separation efficiency of the systems investigated in the paper was additionally confirmed by the separation of test component mixture composed of six hormones. 2010 Elsevier B.V. All rights reserved.

Phase behaviour of disordered proteins underlying low density and high permeability of liquid organelles

NASA Astrophysics Data System (ADS)

Wei, Ming-Tzo; Elbaum-Garfinkle, Shana; Holehouse, Alex S.; Chen, Carlos Chih-Hsiung; Feric, Marina; Arnold, Craig B.; Priestley, Rodney D.; Pappu, Rohit V.; Brangwynne, Clifford P.

2017-11-01

Many intracellular membraneless organelles form via phase separation of intrinsically disordered proteins (IDPs) or regions (IDRs). These include the Caenorhabditis elegans protein LAF-1, which forms P granule-like droplets in vitro. However, the role of protein disorder in phase separation and the macromolecular organization within droplets remain elusive. Here, we utilize a novel technique, ultrafast-scanning fluorescence correlation spectroscopy, to measure the molecular interactions and full coexistence curves (binodals), which quantify the protein concentration within LAF-1 droplets. The binodals of LAF-1 and its IDR display a number of unusual features, including 'high concentration' binodal arms that correspond to remarkably dilute droplets. We find that LAF-1 and other in vitro and intracellular droplets are characterized by an effective mesh size of ∼3-8 nm, which determines the size scale at which droplet properties impact molecular diffusion and permeability. These findings reveal how specific IDPs can phase separate to form permeable, low-density (semi-dilute) liquids, whose structural features are likely to strongly impact biological function.

Liquid-phase and vapor-phase dehydration of organic/water solutions

DOEpatents

Huang, Yu [Palo Alto, CA; Ly, Jennifer [San Jose, CA; Aldajani, Tiem [San Jose, CA; Baker, Richard W [Palo Alto, CA

2011-08-23

Processes for dehydrating an organic/water solution by pervaporation or vapor separation using fluorinated membranes. The processes are particularly useful for treating mixtures containing light organic components, such as ethanol, isopropanol or acetic acid.

Predicting the Fluid-Phase Behavior of Aqueous Solutions of ELP (VPGVG) Sequences Using SAFT-VR.

PubMed

Zhao, Binwu; Lindeboom, Tom; Benner, Steven; Jackson, George; Galindo, Amparo; Hall, Carol K

2017-10-24

The statistical associating fluid theory for potentials of variable range (SAFT-VR) is used to predict the fluid phase behavior of elastin-like polypeptide (ELP) sequences in aqueous solution with special focus on the loci of lower critical solution temperatures (LCSTs). A SAFT-VR model for these solutions is developed following a coarse-graining approach combining information from atomistic simulations and from previous SAFT models for previously reported relevant systems. Constant-pressure temperature-composition phase diagrams are determined for solutions of (VPGVG) n sequences + water with n = 1 to 300. The SAFT-VR equation of state lends itself to the straightforward calculation of phase boundaries so that complete fluid-phase equilibria can be calculated efficiently. A broad range of thermodynamic conditions of temperature and pressure are considered, and regions of vapor-liquid and liquid-liquid coexistence, including LCSTs, are found. The calculated phase boundaries at low concentrations match those measured experimentally. The temperature-composition phase diagrams of the aqueous ELP solutions at low pressure (0.1 MPa) are similar to those of types V and VI phase behavior in the classification of Scott and van Konynenburg. An analysis of the high-pressure phase behavior confirms, however, that a closed-loop liquid-liquid immiscibility region, separate from the gas-liquid envelope, is present for aqueous solutions of (VPGVG) 30 ; such a phase diagram is typical of type VI phase behavior. ELPs with shorter lengths exhibit both liquid-liquid and gas-liquid regions, both of which become less extensive as the chain length of the ELP is decreased. The strength of the hydrogen-bonding interaction is also found to affect the phase diagram of the (VPGVG) 30 system in that the liquid-liquid and gas-liquid regions expand as the hydrogen-bonding strength is decreased and shrink as it is increased. The LCSTs of the mixtures are seen to decrease as the ELP chain length is increased.

Heat Pipe with Axial Wick

NASA Technical Reports Server (NTRS)

Ambrose, Jay H. (Inventor); Holmes, Rolland (Inventor)

2016-01-01

A heat pipe has an evaporator portion, a condenser portion, and at least one flexible portion that is sealingly coupled between the evaporator portion and the condenser portion. The flexible portion has a flexible tube and a flexible separator plate held in place within the flexible tube so as to divide the flexible tube into a gas-phase passage and a liquid-phase artery. The separator plate and flexible tube are configured such that the flexible portion is flexible in a plane that is perpendicular to the separator plate.

Identification of Gravity-Related Effects on Crystal Growth From Melts With an Immiscibility Gap

NASA Technical Reports Server (NTRS)

Kassemi, M.; Sayir, A.; Farmer, S.

1999-01-01

This work involves an experimental-numerical approach to study the effects of natural and Marangoni convections on solidification of single crystals from a silicate melt with a liquid-liquid immiscibility gap. Industrial use of crystals grown from silicate melts is becoming increasingly important in electronic, optical, and high temperature structural applications. Even the simplest silicate systems like Al203-SiO2 have had, and will continue to have, a significant role in the development of traditional and advanced ceramics. A unique feature of crystals grown from the silicate systems is their outstanding linear electro-optic properties. They also exhibit exceptionally high optical rotativity. As a result, these crystals are attractive materials for dielectric, optical, and microwave applications. Experimental work in our laboratory has indicated that directional solidification of a single crystal mullite appears to be preceded by liquid-liquid phase separation in the melt. Disruption of the immiscible state results in crystallization of a two phase structure. There is also evidence that mixing in the melt caused by density-driven convection can significantly affect the stability of the immiscible liquid layers and result in poly-crystalline growth. On earth, the immiscible state has only been observed for small diameter crystals grown in float zone systems where natural convection is almost negligible. Therefore, it is anticipated that growth of large single crystals from silicate melts would benefit from microgravity conditions because of the reduction of the natural convective mixing. The main objective of this research is to determine the effects of transport processes on the phase separation in the melt during growth of a single crystal while addressing the following issues: (1) When do the immiscible layers form and are they real?; (2) What are the main physical characteristics of the immiscible liquids?; and (3) How mixing by natural or Marangoni convection affects the stability of the phase separated melt.

Helium dilution refrigeration system

DOEpatents

Roach, Patrick R.; Gray, Kenneth E.

1988-01-01

A helium dilution refrigeration system operable over a limited time period, and recyclable for a next period of operation. The refrigeration system is compact with a self-contained pumping system and heaters for operation of the system. A mixing chamber contains .sup.3 He and .sup.4 He liquids which are precooled by a coupled container containing .sup.3 He liquid, enabling the phase separation of a .sup.3 He rich liquid phase from a dilute .sup.3 He-.sup.4 He liquid phase which leads to the final stage of a dilution cooling process for obtaining low temperatures. The mixing chamber and a still are coupled by a fluid line and are maintained at substantially the same level with the still cross sectional area being smaller than that of the mixing chamber. This configuration provides maximum cooling power and efficiency by the cooling period ending when the .sup.3 He liquid is depleted from the mixing chamber with the mixing chamber nearly empty of liquid helium, thus avoiding unnecessary and inefficient cooling of a large amount of the dilute .sup.3 He-.sup.4 He liquid phase.

Helium dilution refrigeration system

DOEpatents

Roach, P.R.; Gray, K.E.

1988-09-13

A helium dilution refrigeration system operable over a limited time period, and recyclable for a next period of operation is disclosed. The refrigeration system is compact with a self-contained pumping system and heaters for operation of the system. A mixing chamber contains [sup 3]He and [sup 4]He liquids which are precooled by a coupled container containing [sup 3]He liquid, enabling the phase separation of a [sup 3]He rich liquid phase from a dilute [sup 3]He-[sup 4]He liquid phase which leads to the final stage of a dilution cooling process for obtaining low temperatures. The mixing chamber and a still are coupled by a fluid line and are maintained at substantially the same level with the still cross sectional area being smaller than that of the mixing chamber. This configuration provides maximum cooling power and efficiency by the cooling period ending when the [sup 3]He liquid is depleted from the mixing chamber with the mixing chamber nearly empty of liquid helium, thus avoiding unnecessary and inefficient cooling of a large amount of the dilute [sup 3]He-[sup 4]He liquid phase. 2 figs.

Interaction between phases in the liquid–gas system

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

Berry, R. S., E-mail: bmsmirnov@gmail.com; Smirnov, B. M.

This work analyzes the equilibrium between a liquid and a gas over this liquid separated by an interface. Various gas forms exist inside the liquid: dissolved gas molecules attached to solvent molecules, free gas molecules, and gaseous bubbles. Thermodynamic equilibrium is maintained between two phases; the first phase is the liquid containing dissolved and free molecules, and the second phase is the gas over the liquid and bubbles inside it. Kinetics of gas transition between the internal and external gas proceeds through bubbles and includes the processes of bubbles floating up and bubble growth as a result of association duemore » to the Smoluchowski mechanism. Evolution of a gas in the liquid is considered using the example of oxygen in water, and numerical parameters of this system are given. In the regime under consideration for an oxygen–water system, transport of oxygen into the surrounding air proceeds through micron-size bubbles with lifetimes of hours. This regime is realized if the total number of oxygen molecules in water is small compared with the numbers of solvated and free molecules in the liquid.« less

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.

Symmetry-protected topological phases of one-dimensional interacting fermions with spin-charge separation

NASA Astrophysics Data System (ADS)

Montorsi, Arianna; Dolcini, Fabrizio; Iotti, Rita C.; Rossi, Fausto

2017-06-01

The low energy behavior of a huge variety of one-dimensional interacting spinful fermionic systems exhibits spin-charge separation, described in the continuum limit by two sine-Gordon models decoupled in the charge and spin channels. Interaction is known to induce, besides the gapless Luttinger liquid phase, eight possible gapped phases, among which are the Mott, Haldane, charge-/spin-density, and bond-ordered wave insulators, and the Luther Emery liquid. Here we prove that some of these physically distinct phases have nontrivial topological properties, notably the presence of degenerate protected edge modes with fractionalized charge/spin. Moreover, we show that the eight gapped phases are in one-to-one correspondence with the symmetry-protected topological (SPT) phases classified by group cohomology theory in the presence of particle-hole symmetry P. The latter result is also exploited to characterize SPT phases by measurable nonlocal order parameters which follow the system evolution to the quantum phase transition. The implications on the appearance of exotic orders in the class of microscopic Hubbard Hamiltonians, possibly without P symmetry at higher energies, are discussed.

[Separation of purines, pyrimidines, pterins and flavonoids on magnolol-bonded silica gel stationary phase by high performance liquid chromatography].

PubMed

Chen, Hong; Li, Laishen; Zhang, Yang; Zhou, Rendan

2012-10-01

A new magnolol-bonded silica gel stationary phase (MSP) was used to separate the basic drugs including four purines, eight pyrimidines, four pterins and five flavonoids as polar representative samples by high performance liquid chromatography (HPLC). To clarify the separation mechanism, a commercial ODS column was also tested under the same chromatographic conditions. The high selectivities and fast baseline separations of the above drugs were achieved by using simple mobile phases on MSP. Although there is no end-caped treatment, the peak shapes of basic drugs containing nitrogen such as purines, pyrimidines and pterins were rather symmetrical on MSP, which indicated the the magnolol as ligand with multi-sites could shield the side effect of residual silanol groups on the surface of silica gel. Although somewhat different in the separation resolution, it was found that the elution orders of some drugs were generally similar on both MSP and ODS. The hydrophobic interaction should play a significant role in the separations of the above basic drugs, which was attributed to their reversed-phase property in the nature. However, MSP could provide the additional sites for many polar solutes, which was a rational explanation for the high selectivity of MSP. For example, in the separation of purines, pyrimidines and pterins on MSP, hydrogen-bonding and dipole-dipole interactions played leading roles besides hydrophobic interaction. Some solute molecules (such as mercaptopurine, vitexicarpin) and MSP can form the strong pi-pi stacking in the separation process. All enhanced the retention and improved the separation selectivity of MSP, which facilitated the separation of the basic drugs.

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.

DESIGN AND DEVELOPMENT OF GAS-LIQUID CYLINDRICAL CYCLONE COMPACT SEPARATORS FOR THREE-PHASE FLOW

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

Dr. Ram S. Mohan; Dr. Ovadia Shoham

The U.S. Department of Energy (DOE) has awarded a five-year (1997-2002) grant (Mohan and Shoham, DE-FG26-97BC15024, 1997) to The University of Tulsa, to develop compact multiphase separation components for 3-phase flow. The research activities of this project have been conducted through cost sharing by the member companies of the Tulsa University Separation Technology Projects (TUSTP) research consortium and the Oklahoma Center for the Advancement of Science and Technology (OCAST). As part of this project, several individual compact separation components have been developed for onshore and offshore applications. These include gas-liquid cylindrical cyclones (GLCC{copyright}), liquid-liquid cylindrical cyclones (LLCC{copyright}), and the gas-liquid-liquidmore » cylindrical cyclones (GLLCC{copyright}). A detailed study has also been completed for the liquid-liquid hydrocyclones (LLHC). Appropriate control strategies have been developed for proper operation of the GLCC{copyright} and LLCC{copyright}. Testing of GLCC{copyright} at high pressure and real crude conditions for field applications is also completed. Limited studies have been conducted on flow conditioning devices to be used upstream of the compact separators for performance improvement. This report presents a brief overview of the activities and tasks accomplished during the 5-year project period, October 1, 1997-March 31, 2003 (including the no-cost extended period of 6 months). An executive summary is presented initially followed by the tasks of the 5-year budget periods. Then, detailed description of the experimental and modeling investigations are presented. Subsequently, the technical and scientific results of the activities of this project period are presented with some discussions. The findings of this investigation are summarized in the ''Conclusions'' section, followed by relevant references. The publications resulting from this study in the form of MS Theses, Ph.D. Dissertation, Journal Papers and Conference Presentations are provided at the end of this report.« less

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.

Ionic liquids as stationary phases for fatty acid analysis by gas chromatography.

PubMed

Fanali, C; Micalizzi, G; Dugo, P; Mondello, L

2017-12-04

The present paper provides an overview of the application of ionic liquid (IL) columns for GC analysis of fatty acid methyl esters (FAMEs). Although their separation can be carried out utilizing GC columns containing polar stationary phases, some ILs have been employed as stationary phases, either commercial or laboratory made, in GC analysis. Monodimensional and bidimensional GC methods have been optimized in order to achieve the best separation especially considering the geometric and positional isomers of unsaturated fatty acids. Several methods for the analysis of trans-fatty acids have also been reported. The use of GC-GC, using either the same IL columns or different columns in the first and second dimensions, allowed the separation of a large number of FAMEs. The application of the IL columns for GC analysis of FAMEs in different types of real samples is described, e.g., oil of different nature (fish, flaxseed, and olive), margarine and butter, biodiesel, milk, bacteria etc.

Binding Affinity Effects on Physical Characteristics of a Model Phase-Separated Protein Droplet

NASA Astrophysics Data System (ADS)

Chuang, Sara; Banani, Salman; Rosen, Michael; Brangwynne, Clifford

2015-03-01

Non-membrane bound organelles are associated with a range of biological functions. Several of these structures exhibit liquid-like properties, and may represent droplets of phase-separated RNA and/or proteins. These structures are often enriched in multi-valent molecules, however little is known about the interactions driving the assembly, properties, and function. Here, we address this question using a model multi-valent protein system consisting of repeats of Small Ubiquitin-like Modifier (SUMO) protein and a SUMO-interacting motif (SIM). These proteins undergo phase separation into liquid-like droplets. We combine microrheology and quantitative microscopy to determine affect of binding affinity on the viscosity, density and surface tension of these droplets. We also use fluorescence recovery after photobleaching (FRAP), fluorescence correlation spectroscopy (FCS) and partitioning experiments to probe the structure and dynamics within these droplets. Our results shed light on how inter-molecular interactions manifests in droplet properties, and lay the groundwork for a comprehensive biophysical picture of intracellular RNA/protein organelles.

[Chiral separation of five beta-blockers using di-n-hexyl L-tartrate-boric acid complex as mobile phase additive by reversed-phase liquid chromatography].

PubMed

Yang, Juan; Wang, Lijuan; Guo, Qiaoling; Yang, Gengliang

2012-03-01

A reversed-phase high performance liquid chromatographic (HPLC) method using the di-n-hexyl L-tartrate-boric acid complex as a chiral mobile phase additive was developed for the enantioseparation of five beta-blockers including propranolol, esmolol, metoprolol, bisoprolol and sotalol. In order to obtain a better enantioseparation, the influences of concentrations of di-n-butyl L-tartrate and boric acid, the type, concentration and pH of the buffer, methanol content as well as the molecular structure of analytes were extensively investigated. The separation of the analytes was performed on a Venusil MP-C18 column (250 mm x 4.6 mm, 5 microm). The mobile phase was 15 mmol/L ammonium acetate-methanol containing 60 mmol/L boric acid, 70 mmol/L di-n-hexyl L-tartrate (pH 6.00). The volume ratios of 15 mmol/L ammonium acetate to methanol were 20: 80 for propranolol, esmolol, metoprolol, bisoprolol and 30: 70 for sotalol. The flow rate was 0.5 mL/min and the detection wavelength was set at 214 nm. Under the optimized conditions, baseline enantioseparation was obtained separately for the five pairs of analytes.

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.

Chiral HPLC for a study of the optical purity of new liquid crystalline materials derived from lactic acid

NASA Astrophysics Data System (ADS)

Vojtylová, T.; Kašpar, M.; Hamplová, V.; Novotná, V.; Sýkora, D.

2014-08-01

New liquid crystalline (LC) materials were prepared by derivatization of lactic acid. First compound possesses the lactic acid unit as the only chiral center and the second group of LC materials contains two chiral centers. Mesomorphic properties of both the newly synthesized LC materials were studied and the presence of the SmA*-SmC* or exhibit the twist grain boundary (TGB) phases, namely TGBA and TGBC, in a wide range of temperatures down to the room temperature was established. The potential of high-performance liquid chromatography (HPLC) applying chiral stationary phases to separate enantiomers or diastereoisomers of the synthesized LC compounds was evaluated. Two different brands of commercial chiral sorbents, Lux Amylose-2 and Chiralpak AD-3, both based on modified silica with derivatized polysaccharide, were employed in the development of separation procedures. The optimized chiral HPLC method provided a baseline separation of the individual enantiomers for the LC material containing one chiral center. In the case of the more complex compound with two asymmetric carbon atoms, where four isomers exist, partial separation was reached only using the current chiral HPLC.

Life Cycle Assessment of an Ionic LIquid versus Traditional Solvents and Their Applications

EPA Science Inventory

Ionic liquids (ILs) have been claimed as "greener" replacements to traditional solvents. HOwever, the environmental impacts of the life cycle phases including the making of ILs, their application, separation, etc., and comparison with alternative methods have not been studied. Su...

Two-phase anaerobic digestion of vegetable market waste fraction of municipal solid waste and development of improved technology for phase separation in two-phase reactor.

PubMed

Majhi, Bijoy Kumar; Jash, Tushar

2016-12-01

Biogas production from vegetable market waste (VMW) fraction of municipal solid waste (MSW) by two-phase anaerobic digestion system should be preferred over the single-stage reactors. This is because VMW undergoes rapid acidification leading to accumulation of volatile fatty acids and consequent low pH resulting in frequent failure of digesters. The weakest part in the two-phase anaerobic reactors was the techniques applied for solid-liquid phase separation of digestate in the first reactor where solubilization, hydrolysis and acidogenesis of solid organic waste occur. In this study, a two-phase reactor which consisted of a solid-phase reactor and a methane reactor was designed, built and operated with VMW fraction of Indian MSW. A robust type filter, which is unique in its implementation method, was developed and incorporated in the solid-phase reactor to separate the process liquid produced in the first reactor. Experiments were carried out to assess the long term performance of the two-phase reactor with respect to biogas production, volatile solids reduction, pH and number of occurrence of clogging in the filtering system or choking in the process liquid transfer line. The system performed well and was operated successfully without the occurrence of clogging or any other disruptions throughout. Biogas production of 0.86-0.889m 3 kg -1 VS, at OLR of 1.11-1.585kgm -3 d -1 , were obtained from vegetable market waste, which were higher than the results reported for similar substrates digested in two-phase reactors. The VS reduction was 82-86%. The two-phase anaerobic digestion system was demonstrated to be stable and suitable for the treatment of VMW fraction of MSW for energy generation. Copyright © 2016 Elsevier Ltd. All rights reserved.

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.

Flame spread across liquid pools

NASA Technical Reports Server (NTRS)

Ross, Howard; Miller, Fletcher; Schiller, David; Sirignano, William A.

1993-01-01

For flame spread over liquid fuel pools, the existing literature suggests three gravitational influences: (1) liquid phase buoyant convection, delaying ignition and assisting flame spread; (2) hydrostatic pressure variation, due to variation in the liquid pool height caused by thermocapillary-induced convection; and (3) gas-phase buoyant convection in the opposite direction to the liquid phase motion. No current model accounts for all three influences. In fact, prior to this work, there was no ability to determine whether ignition delay times and flame spread rates would be greater or lesser in low gravity. Flame spread over liquid fuel pools is most commonly characterized by the relationship of the initial pool temperature to the fuel's idealized flash point temperature, with four or five separate characteristic regimes having been identified. In the uniform spread regime, control has been attributed to: (1) gas-phase conduction and radiation; (2) gas-phase conduction only; (3) gas-phase convection and liquid conduction, and most recently (4) liquid convection ahead of the flame. Suggestions were made that the liquid convection was owed to both vuoyancy and thermocapillarity. Of special interest to this work is the determination of whether, and under what conditions, pulsating spread can and will occur in microgravity in the absence of buoyant flows in both phases. The approach we have taken to resolving the importance of buoyancy for these flames is: (1) normal gravity experiments and advanced diagnostics; (2) microgravity experiments; and (3) numerical modelling at arbitrary gravitational level.

Coal liquefaction quenching process

DOEpatents

Thorogood, Robert M.; Yeh, Chung-Liang; Donath, Ernest E.

1983-01-01

There is described an improved coal liquefaction quenching process which prevents the formation of coke with a minimum reduction of thermal efficiency of the coal liquefaction process. In the process, the rapid cooling of the liquid/solid products of the coal liquefaction reaction is performed without the cooling of the associated vapor stream to thereby prevent formation of coke and the occurrence of retrograde reactions. The rapid cooling is achieved by recycling a subcooled portion of the liquid/solid mixture to the lower section of a phase separator that separates the vapor from the liquid/solid products leaving the coal reactor.

Solid-liquid critical behavior of water in nanopores.

PubMed

Mochizuki, Kenji; Koga, Kenichiro

2015-07-07

Nanoconfined liquid water can transform into low-dimensional ices whose crystalline structures are dissimilar to any bulk ices and whose melting point may significantly rise with reducing the pore size, as revealed by computer simulation and confirmed by experiment. One of the intriguing, and as yet unresolved, questions concerns the observation that the liquid water may transform into a low-dimensional ice either via a first-order phase change or without any discontinuity in thermodynamic and dynamic properties, which suggests the existence of solid-liquid critical points in this class of nanoconfined systems. Here we explore the phase behavior of a model of water in carbon nanotubes in the temperature-pressure-diameter space by molecular dynamics simulation and provide unambiguous evidence to support solid-liquid critical phenomena of nanoconfined water. Solid-liquid first-order phase boundaries are determined by tracing spontaneous phase separation at various temperatures. All of the boundaries eventually cease to exist at the critical points and there appear loci of response function maxima, or the Widom lines, extending to the supercritical region. The finite-size scaling analysis of the density distribution supports the presence of both first-order and continuous phase changes between solid and liquid. At around the Widom line, there are microscopic domains of two phases, and continuous solid-liquid phase changes occur in such a way that the domains of one phase grow and those of the other evanesce as the thermodynamic state departs from the Widom line.

Paired-ion chromatography and high performance liquid chromatography of labetalol in feeds.

PubMed

Townley, E R; Ross, B

1980-11-01

A high performance liquid chromatographic (HPLC) method using reverse phase paired-ion chromatography and ultraviolet detection at 280 nm has been developed to determine labetalol, an alpha and beta adrenoceptor blocking agent, in Purina No. 5001 rodent chow. The method is simple and rapid, and demonstrates a separation technique applicable to other acidic and basic drugs. It requires only extraction of the drug with methanol--water--acetic acid (66 + 33 + 1) and separation of insoluble material by filtration before HPLC. Labetalol, is chromatographically separated from soluble feed components by means of a microBondapak C18 column and methanol--water--acetic acid (66 + 33 + 1) mobile phase, 0.005M with respect to sodium dioctylsulfosuccinate paired-ion reagent. Average recovery is 98.7% with a relative standard deviation of +/- 2.3% for the equipment described.

Widom Lines in Binary Mixtures of Supercritical Fluids.

PubMed

Raju, Muralikrishna; Banuti, Daniel T; Ma, Peter C; Ihme, Matthias

2017-06-08

Recent experiments on pure fluids have identified distinct liquid-like and gas-like regimes even under supercritical conditions. The supercritical liquid-gas transition is marked by maxima in response functions that define a line emanating from the critical point, referred to as Widom line. However, the structure of analogous state transitions in mixtures of supercritical fluids has not been determined, and it is not clear whether a Widom line can be identified for binary mixtures. Here, we present first evidence for the existence of multiple Widom lines in binary mixtures from molecular dynamics simulations. By considering mixtures of noble gases, we show that, depending on the phase behavior, mixtures transition from a liquid-like to a gas-like regime via distinctly different pathways, leading to phase relationships of surprising complexity and variety. Specifically, we show that miscible binary mixtures have behavior analogous to a pure fluid and the supercritical state space is characterized by a single liquid-gas transition. In contrast, immiscible binary mixture undergo a phase separation in which the clusters transition separately at different temperatures, resulting in multiple distinct Widom lines. The presence of this unique transition behavior emphasizes the complexity of the supercritical state to be expected in high-order mixtures of practical relevance.

Evolution of a phase separated gravity independent bioreactor

NASA Technical Reports Server (NTRS)

Villeneuve, Peter E.; Dunlop, Eric H.

1992-01-01

The evolution of a phase-separated gravity-independent bioreactor is described. The initial prototype, a zero head-space manifold silicone membrane based reactor, maintained large diffusional resistances. Obtaining oxygen transfer rates needed to support carbon-recycling aerobic microbes is impossible if large resistances are maintained. Next generation designs (Mark I and II) mimic heat exchanger design to promote turbulence at the tubing-liquid interface, thereby reducing liquid and gas side diffusional resistances. While oxygen transfer rates increased by a factor of ten, liquid channeling prevented further increases. To overcome these problems, a Mark III reactor was developed which maintains inverted phases, i.e., media flows inside the silicone tubing, oxygen gas is applied external to the tubing. This enhances design through changes in gas side driving force concentration and liquid side turbulence levels. Combining an applied external pressure of 4 atm with increased Reynolds numbers resulted in oxygen transfer intensities of 232 mmol O2/l per hr (1000 times greater than the first prototype and comparable to a conventional fermenter). A 1.0 liter Mark III reactor can potentially deliver oxygen supplies necessary to support cell cultures needed to recycle a 10-astronaut carbon load continuously.

Determination of fenoterol in human plasma by HPLC with fluorescence detection after derivatization.

PubMed

Meineke, Ingolf; Steinmetz, Hannelore; Kramer, Skaidrit; Gleiter, Christoph H

2002-06-20

A new method for the determination of fenoterol is described, which uses HPLC separation with fluorescence detection. Dobutamine is employed as an internal standard. The separation was achieved on a short reversed phase column with a mobile phase consisting of water, acetonitrile and methanol. Prior to chromatography both analytes are derivatized with 9-chloroformyl-carbazole. Isolation of the analytes from plasma is carried out by liquid-liquid extraction into 2-butanol after protein precipitation with acetonitrile. The method is capable of estimating fenoterol concentrations in the sub-nanogram per ml range with sufficient accuracy and precision. The determination of fenoterol can now be carried out in the average laboratory without radiolabelled material.

Magnetic ionic liquid aqueous two-phase system coupled with high performance liquid chromatography: A rapid approach for determination of chloramphenicol in water environment.

PubMed

Yao, Tian; Yao, Shun

2017-01-20

A novel organic magnetic ionic liquid based on guanidinium cation was synthesized and characterized. A new method of magnetic ionic liquid aqueous two-phase system (MILATPs) coupled with high-performance liquid chromatography (HPLC) was established to preconcentrate and determine trace amount of chloramphenicol (CAP) in water environment for the first time. In the absence of volatile organic solvents, MILATPs not only has the excellent properties of rapid extraction, but also exhibits a response to an external magnetic field which can be applied to assist phase separation. The phase behavior of MILATPs was investigated and phase equilibrium data were correlated by Merchuk equation. Various influencing factors on CAP recovery were systematically investigated and optimized. Under the optimal conditions, the preconcentration factor was 147.2 with the precision values (RSD%) of 2.42% and 4.45% for intra-day (n=6) and inter-day (n=6), respectively. The limit of detection (LOD) and limit of quantitation (LOQ) were 0.14ngmL -1 and 0.42ngmL -1 , respectively. Fine linear range of 12.25ngmL -1 -2200ngmL -1 was obtained. Finally, the validated method was successfully applied for the analysis of CAP in some environmental waters with the recoveries for the spiked samples in the acceptable range of 94.6%-99.72%. Hopefully, MILATPs is showing great potential to promote new development in the field of extraction, separation and pretreatment of various biochemical samples. Copyright © 2016 Elsevier B.V. All rights reserved.

Characterization of van der Waals type bimodal,- lambda,- meta- and spinodal phase transitions in liquid mixtures, solid suspensions and thin films.

PubMed

Rosenholm, Jarl B

2018-03-01

The perfect gas law is used as a reference when selecting state variables (P, V, T, n) needed to characterize ideal gases (vapors), liquids and solids. Van der Waals equation of state is used as a reference for models characterizing interactions in liquids, solids and their mixtures. Van der Waals loop introduces meta- and unstable states between the observed gas (vapor)-liquid P-V transitions at low T. These intermediate states are shown to appear also between liquid-liquid, liquid-solid and solid-solid phase transitions. First-order phase transitions are characterized by a sharp discontinuity of first-order partial derivatives (P, S, V) of Helmholtz and Gibbs free energies. Second-order partial derivatives (K T , B, C V , C P , E) consist of a static contribution relating to second-order phase transitions and a relaxation contribution representing the degree of first-order phase transitions. Bimodal (first-order) and spinodal (second-order) phase boundaries are used to separate stable phases from metastable and unstable phases. The boundaries are identified and quantified by partial derivatives of molar Gibbs free energy or chemical potentials with respect to P, S, V and composition (mole fractions). Molecules confined to spread Langmuir monolayers or adsorbed Gibbs monolayers are characterized by equation of state and adsorption isotherms relating to a two-dimensional van der Waals equation of state. The basic work of two-dimensional wetting (cohesion, adsorption, spreading, immersion), have to be adjusted by a horizontal surface pressure in the presence of adsorbed vapor layers. If the adsorption is extended to liquid films a vertical surface pressure (Π) may be added to account for the lateral interaction, thus restoring PV = ΠAh dependence of thin films. Van der Waals attraction, Coulomb repulsion and structural hydration forces contribute to the vertical surface pressure. A van der Waals type coexistence of ordered (dispersed) and disordered (aggregated) phases is shown to exist when liquid vapor is confined in capillaries (condensation-liquefaction-evaporation and flux). This pheno-menon can be experimentally illustrated with suspended nano-sized particles (flocculation-coagulation-peptisation of colloidal sols) being confined in sample holders of varying size. The self-assembled aggregates represent critical self-similar equilibrium structures corres-ponding to rate determining complexes in kinetics. Overall, a self-consistent thermodynamic framework is established for the characterization of two- and three-dimensional phase separations in one-, two- and three-component systems. Copyright © 2018 Elsevier B.V. All rights reserved.

Control of disinfection by-products in canned vegetables caused by water used in their processing.

PubMed

Cardador, Maria Jose; Gallego, Mercedes

2017-01-01

Canned vegetables come into contact with sanitizers and/or treated water in industry during several steps (namely washing, sanitising, blanching and filling with sauces or brine solutions) and therefore they can contain disinfection by-products - DBPs). This study focused on the occurrence of trihalomethanes (THMs) and haloacetic acids (HAAs) in a wide variety of canned vegetables (75 samples). For each vegetable, the edible solid and liquid phases of the package were separated and analysed individually. DBPs can be present in both solid (up to eight species) and liquid (up to 11 species) phases, their levels being higher in liquid ones. Volatile THMs predominate in the edible solid phase (up to four species), while HAAs do so in the liquid phase (up to five species) according to their ionic and non-volatile nature. The lowest concentrations of DBPs were found in tomatoes because they were often preserved in their own juice, without water.

Wetting Transitions in ^4He/^3He Mixtures on Cesium

NASA Astrophysics Data System (ADS)

Ross, David

1997-03-01

Over the last several years, helium on cesium has proven to be an ideal model system for the study of wetting and wetting transitions(E. Cheng, M.W. Cole, W.F. Saam, and J. Treiner, Phys. Rev. Lett. 67), 1007 (1991).^,(J.E. Rutledge and P. Taborek, Phys. Rev. Lett. 69), 937 (1992).^,(D. Ross, J.E. Rutledge, and P. Taborek, Phys. Rev. Lett. 76), 2350 (1996).. This presentation will focus on the adsorption of binary liquid mixtures of the helium isotopes, ^3He and ^4He, on cesium substrates over a range of temperatures extending from 0.2 K to 1.0 K. The results, spanning ^3He concentrations from 0 to 1, constitute the first experimentally constructed complete wetting phase diagram for a two component liquid at a weakly binding substrate. The wetting behavior is particularly interesting in the vicinity of bulk liquid phase separation. A wetting transition of the ^4He rich liquid between the ^3He rich liquid and the cesium substrate has been found with Tw = 0.53 K. The surface phase transition line associated with this wetting transition is found to extend to both sides of the bulk phase separation line. On the ^3He rich side it is a prewetting line, and on the ^4He rich side it becomes a line of triple point induced dewetting transitions. General arguments indicate that this behavior should be typical of a large class of binary liquid mixtures at weakly binding substrates.

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.

FAST TRACK COMMUNICATION: Gas liquid phase coexistence in a tetrahedral patchy particle model

NASA Astrophysics Data System (ADS)

Romano, Flavio; Tartaglia, Piero; Sciortino, Francesco

2007-08-01

We evaluate the location of the gas-liquid coexistence line and of the associated critical point for the primitive model for water (PMW), introduced by Kolafa and Nezbeda (1987 Mol. Phys. 61 161). Besides being a simple model for a molecular network forming liquid, the PMW is representative of patchy proteins and novel colloidal particles interacting with localized directional short-range attractions. We show that the gas-liquid phase separation is metastable, i.e. it takes place in the region of the phase diagram where the crystal phase is thermodynamically favoured, as in the case of particles interacting via short-range attractive spherical potentials. We do not observe crystallization close to the critical point. The region of gas-liquid instability of this patchy model is significantly reduced as compared to that from equivalent models of spherically interacting particles, confirming the possibility of observing kinetic arrest in a homogeneous sample driven by bonding as opposed to packing.

Colloidal mode of transport in the Potomac River watershed

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

Maher, I.L.; Foster, G.D.

1995-12-31

Similarly to the particulate phase the colloidal phase may play an important role in the organic contaminant transport downstream the river. The colloidal phase consisting of microparticles and micromolecules which are small enough to be mobile and large enough to attract pollutants can absorb nonpolar organic compounds similarly as do soil and sediment particles. To test the hypothesis three river water samples have been analyzed for PAH content in the dissolved, the colloidal, and the particulate phase. The first sample was collected at the Blue Ridge province of Potomac River watershed, at Point of Rocks, the second one in themore » Pidmont province, at Riverbend Park, and the third sample at Coastal Plane, at Dyke Marsh (Belle Heven marina). In the laboratory environment each water sample was prefiltered to separate the particulate phase form the dissolved and colloidal phase. One part of the prefiltered water sample was ultrafiltered to separate colloids while the second part of the water was Goulden extracted. The separated colloidal phase was liquid-liquid extracted (LLE) while filters containing the suspended solids were Soxhlet extracted. The extracts of the particulate phase, the colloidal phase, and the dissolved plus colloidal phase were analyzed for selected PAHs via GC/MS. It is planned that concentrations of selected PAHs in three phases will be used for calculations of the partition coefficients, the colloid/dissolved partition coefficient and the particle/dissolved partition coefficient. Both partition coefficients will be compared to define the significance of organic contaminant transport by aquatic colloids.« less

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.

Self-Supporting, Hydrophobic, Ionic Liquid-Based Reference Electrodes Prepared by Polymerization-Induced Microphase Separation.

PubMed

Chopade, Sujay A; Anderson, Evan L; Schmidt, Peter W; Lodge, Timothy P; Hillmyer, Marc A; Bühlmann, Philippe

2017-10-27

Interfaces of ionic liquids and aqueous solutions exhibit stable electrical potentials over a wide range of aqueous electrolyte concentrations. This makes ionic liquids suitable as bridge materials that separate in electroanalytical measurements the reference electrode from samples with low and/or unknown ionic strengths. However, methods for the preparation of ionic liquid-based reference electrodes have not been explored widely. We have designed a convenient and reliable synthesis of ionic liquid-based reference electrodes by polymerization-induced microphase separation. This technique allows for a facile, single-pot synthesis of ready-to-use reference electrodes that incorporate ion conducting nanochannels filled with either 1-octyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide or 1-dodecyl-3-methylimidazolium bis(trifluoromethyl sulfonyl)imide as ionic liquid, supported by a mechanically robust cross-linked polystyrene phase. This synthesis procedure allows for the straightforward design of various reference electrode geometries. These reference electrodes exhibit a low resistance as well as good reference potential stability and reproducibility when immersed into aqueous solutions varying from deionized, purified water to 100 mM KCl, while requiring no correction for liquid junction potentials.

On the implications of aerosol liquid water and phase separation for organic aerosol mass

EPA Science Inventory

Organic compounds and liquid water are major aerosol constituents in the southeast United States (SE US). Water associated with inorganic constituents (inorganic water) can contribute to the partitioning medium for organic aerosol when relative humidities or organic matter to org...

Quantitation of triacylglycerols in edible oils by off-line comprehensive two-dimensional liquid chromatography-atmospheric pressure chemical ionization mass spectrometry using a single column.

PubMed

Wei, Fang; Hu, Na; Lv, Xin; Dong, Xu-Yan; Chen, Hong

2015-07-24

In this investigation, off-line comprehensive two-dimensional liquid chromatography-atmospheric pressure chemical ionization mass spectrometry using a single column has been applied for the identification and quantification of triacylglycerols in edible oils. A novel mixed-mode phenyl-hexyl chromatographic column was employed in this off-line two-dimensional separation system. The phenyl-hexyl column combined the features of traditional C18 and silver-ion columns, which could provide hydrophobic interactions with triacylglycerols under acetonitrile conditions and can offer π-π interactions with triacylglycerols under methanol conditions. When compared with traditional off-line comprehensive two-dimensional liquid chromatography employing two different chromatographic columns (C18 and silver-ion column) and using elution solvents comprised of two phases (reversed-phase/normal-phase) for triacylglycerols separation, the novel off-line comprehensive two-dimensional liquid chromatography using a single column can be achieved by simply altering the mobile phase between acetonitrile and methanol, which exhibited a much higher selectivity for the separation of triacylglycerols with great efficiency and rapid speed. In addition, an approach based on the use of response factor with atmospheric pressure chemical ionization mass spectrometry has been developed for triacylglycerols quantification. Due to the differences between saturated and unsaturated acyl chains, the use of response factors significantly improves the quantitation of triacylglycerols. This two-dimensional liquid chromatography-mass spectrometry system was successfully applied for the profiling of triacylglycerols in soybean oils, peanut oils and lord oils. A total of 68 triacylglycerols including 40 triacylglycerols in soybean oils, 50 triacylglycerols in peanut oils and 44 triacylglycerols in lord oils have been identified and quantified. The liquid chromatography-mass spectrometry data were analyzed using principal component analysis. The results of the principal component analysis enabled a clear identification of different plant oils. By using this two-dimensional liquid chromatography-mass spectrometry system coupled with principal component analysis, adulterated soybean oils with 5% added lord oil and peanut oils with 5% added soybean oil can be clearly identified. Copyright © 2015 Elsevier B.V. All rights reserved.

Ultrasound-assisted analyte extraction for the determination of sulfate and elemental sulfur in zinc sulfide by different liquid chromatography techniques.

PubMed

Dash, K; Thangavel, S; Krishnamurthy, N V; Rao, S V; Karunasagar, D; Arunachalam, J

2005-04-01

The speciation and determination of sulfate (SO4(2-)) and elemental sulfur (S degree) in zinc sulfide (ZnS) using ion-chromatography (IC) and reversed-phase liquid chromatography (RPLC) respectively is described. Three sample pretreatment approaches were employed with the aim of determining sulfate: (i) conventional water extraction of the analyte; (ii) solid-liquid aqueous extraction with an ultrasonic probe; and (iii) elimination of the zinc sulfide matrix via ion-exchange dissolution (IED). The separation of sulfate was carried out by an anion-exchange column (IonPac AS17), followed by suppressed conductivity detection. Elemental sulfur was extracted ultrasonically from the acid treated sample solution into chloroform and separated on a reversed phase HPLC column equipped with a diode array detector (DAD) at 264 nm. The achievable solid detection limits for sulfate and sulfur were 35 and 10 microg g(-1) respectively.

METHOD OF INHIBITING CORROSION IN URANYL SULFATE SOLUTIONS

DOEpatents

Bohlmann, E.G.; Griess, J.C. Jr.

1960-08-23

A method is given for treating a uranyl sulfate solution to inhibit the corrosiveness of the solution and elevate the phase separation temperature of the solution. Lithium sulfate is added to the solution in an amount ranging from 0.25 to 1.3 times the uranyl sulfate concentration. The corrosiveness of the solution with respect to stainless steel is substantially decreased by this means. This treatment also serves to raise the phase separation temperature of the solution (above 250 deg C), at which time the uranyl sulfate solution separates into two liquid phases of unequal uranium concentration and thus becomes unsuitable as nuclear reactor fuel.

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

PubMed

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

2018-05-30

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

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.

Phase Transitions in the Nucleus: the functional implications of concentration-dependent assembly of a Liquid-like RNA/Protein Body

NASA Astrophysics Data System (ADS)

Zhu, Lian; Weber, Stephanie; Berry, Joel; Vaidya, Nilesh; Haataja, Mikko; Brangwynne, Clifford

2015-03-01

The nucleolus is a liquid-like membrane-less nuclear body which plays an important role in cell growth and size control. By modulating nucleolar component concentration through RNAi conditions that change C. elegans cell size, we find that nucleoli only assemble above a threshold concentration; moreover, the ripening dynamics of nucleated droplets are consistent with the hypothesis that the assembly of the nucleolus represents an intracellular liquid-liquid phase transition. A key question is how this phase-transition is linked to the primary function of the nucleolus, in transcribing and processing ribosomal RNA. To address this, we characterize the localization of RNA Polymerase I, a key transcriptional enzyme, into nucleolar foci as a function of nucleolar component concentration. Our results suggest that there are a small number of key disordered phosphoproteins that may serve as a link between transcription and assembly. Finally, we present preliminary results using a reduced model system consisting of purified nucleolar proteins to assess the ability of nucleolar proteins to drive liquid-liquid phase separation in vitro. These results lay the foundation for a quantitative understanding of intracellular phase transitions and their impact on biomedically-critical RNA-processing steps.

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.

Modern separation techniques coupled to high performance mass spectrometry for glycolipid analysis.

PubMed

Sarbu, Mirela; Zamfir, Alina Diana

2018-01-21

Glycolipids (GLs), involved in biological processes and pathologies, such as viral, neurodegenerative and oncogenic transformations are in the focus of research related to method development for structural analysis. This review highlights modern separation techniques coupled to mass spectrometry (MS) for the investigation of GLs from various biological matrices. First section is dedicated to methods, which, although provide the separation in a non-liquid phase, are able to supply important data on the composition of complex mixtures. While classical thin layer chromatography (TLC) is useful for MS analyses of the fractionated samples, ultramodern ion mobility (IMS) characterized by high reproducibility facilitates to discover minor species and to apply low sample amounts, in addition to providing conformational separation with isomer discrimination. Second section highlights the advantages, applications and limitations of liquid-based separation techniques such as high performance liquid chromatography (HPLC) and hydrophilic interaction liquid chromatography (HILIC) in direct or indirect coupling to MS for glycolipidomics surveys. The on- and off-line capillary electrophoresis (CE) MS, offering a remarkable separation efficiency of GLs is also presented and critically assessed from the technical and application perspective in the final part of the review. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Digital holographic microscopy of phase separation in multicomponent lipid membranes

NASA Astrophysics Data System (ADS)

Farzam Rad, Vahideh; Moradi, Ali-Reza; Darudi, Ahmad; Tayebi, Lobat

2016-12-01

Lateral in-homogeneities in lipid compositions cause microdomains formation and change in the physical properties of biological membranes. With the presence of cholesterol and mixed species of lipids, phospholipid membranes segregate into lateral domains of liquid-ordered and liquid-disordered phases. Coupling of two-dimensional intralayer phase separations and interlayer liquid-crystalline ordering in multicomponent membranes has been previously demonstrated. By the use of digital holographic microscopy (DHMicroscopy), we quantitatively analyzed the volumetric dynamical behavior of such membranes. The specimens are lipid mixtures composed of sphingomyelin, cholesterol, and unsaturated phospholipid, 1,2-dioleoyl-sn-glycero-3-phosphocholine. DHMicroscopy in a transmission mode is an effective tool for quantitative visualization of phase objects. By deriving the associated phase changes, three-dimensional information on the morphology variation of lipid stacks at arbitrary time scales is obtained. Moreover, the thickness distribution of the object at demanded axial planes can be obtained by numerical focusing. Our results show that the volume evolution of lipid domains follows approximately the same universal growth law of previously reported area evolution. However, the thickness of the domains does not alter significantly by time; therefore, the volume evolution is mostly attributed to the changes in area dynamics. These results might be useful in the field of membrane-based functional materials.

Quality by design: a systematic and rapid liquid chromatography and mass spectrometry method for eprosartan mesylate and its related impurities using a superficially porous particle column.

PubMed

Kalariya, Pradipbhai D; Kumar Talluri, Murali V N; Gaitonde, Vinay D; Devrukhakar, Prashant S; Srinivas, Ragampeta

2014-08-01

The present work describes the systematic development of a robust, precise, and rapid reversed-phase liquid chromatography method for the simultaneous determination of eprosartan mesylate and its six impurities using quality-by-design principles. The method was developed in two phases, screening and optimization. During the screening phase, the most suitable stationary phase, organic modifier, and pH were identified. The optimization was performed for secondary influential parameters--column temperature, gradient time, and flow rate using eight experiments--to examine multifactorial effects of parameters on the critical resolution and generated design space representing the robust region. A verification experiment was performed within the working design space and the model was found to be accurate. This study also describes other operating features of the column packed with superficially porous particles that allow very fast separations at pressures available in most liquid chromatography instruments. Successful chromatographic separation was achieved in less than 7 min using a fused-core C18 (100 mm × 2.1 mm, 2.6 μm) column with linear gradient elution of 10 mM ammonium formate (pH 3.0) and acetonitrile as the mobile phase. The method was validated for specificity, linearity, accuracy, precision, and robustness in compliance with the International Conference on Harmonization Q2 (R1) guidelines. The impurities were identified by liquid chromatography with mass spectrometry. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

ELECTRICALLY ACTUATED, PRESSURE-DRIVEN LIQUID CHROMATOGRAPHY SEPARATIONS IN MICROFABRICATED DEVICES

PubMed Central

Fuentes, Hernan V.; Woolley, Adam T.

2012-01-01

Electrolysis-based micropumps integrated with microfluidic channels in micromachined glass substrates are presented. Photolithography combined with wet chemical etching and thermal bonding enabled the fabrication of multi-layer devices containing electrically actuated micropumps interfaced with sample and mobile phase reservoirs. A stationary phase was deposited on the microchannel walls by coating with 10% (w/w) chlorodimethyloctadecylsilane in toluene. Pressure-balanced injection was implemented by controlling the electrolysis time and voltage applied in the two independent micropumps. Current fluctuations in the micropumps due to the stochastic formation of bubbles on the electrode surfaces were determined to be the main cause of variation between separations. On-chip electrochemical pumping enabled the loading of pL samples with no dead volume between injection and separation. A mobile phase composed of 70% acetonitrile and 30% 50 mM acetate buffer (pH 5.45) was used for the chromatographic separation of three fluorescently labeled amino acids in <40 s with an efficiency of >3000 theoretical plates in a 2.5-cm-long channel. Our results demonstrate the potential of electrochemical micropumps integrated with microchannels to perform rapid chromatographic separations in a microfabricated platform. Importantly, these devices represent a significant step toward the development of miniaturized and fully integrated liquid chromatography systems. PMID:17960281

Electrically actuated, pressure-driven liquid chromatography separations in microfabricated devices.

PubMed

Fuentes, Hernan V; Woolley, Adam T

2007-11-01

Electrolysis-based micropumps integrated with microfluidic channels in micromachined glass substrates are presented. Photolithography combined with wet chemical etching and thermal bonding enabled the fabrication of multi-layer devices containing electrically actuated micropumps interfaced with sample and mobile phase reservoirs. A stationary phase was deposited on the microchannel walls by coating with 10% (w/w) chlorodimethyloctadecylsilane in toluene. Pressure-balanced injection was implemented by controlling the electrolysis time and voltage applied in the two independent micropumps. Current fluctuations in the micropumps due to the stochastic formation of bubbles on the electrode surfaces were determined to be the main cause of variation between separations. On-chip electrochemical pumping enabled the loading of pL samples with no dead volume between injection and separation. A mobile phase composed of 70% acetonitrile and 30% 50 mM acetate buffer (pH 5.45) was used for the chromatographic separation of three fluorescently labeled amino acids in <40 s with an efficiency of >3000 theoretical plates in a 2.5 cm-long channel. Our results demonstrate the potential of electrochemical micropumps integrated with microchannels to perform rapid chromatographic separations in a microfabricated platform. Importantly, these devices represent a significant step toward the development of miniaturized and fully integrated liquid chromatography systems.

Pyrene-Tagged Ionic Liquids: Separable Organic Catalysts for SN2 Fluorination.

PubMed

Taher, Abu; Lee, Kyo Chul; Han, Hye Ji; Kim, Dong Wook

2017-07-07

We prepared pyrene-substituted imidazolium-based ionic liquids (PILs) as organic catalysts for the S N 2 fluorination using alkali metal fluoride (MF). In this system, the PIL significantly enhanced the reactivity of MF due to the phase-transfer catalytic effect of the imidazolium moiety as well as the metal cation-π (pyrene) interactions. Furthermore, this homogeneous catalyst PIL was easily separated from the reaction mixture using reduced graphene oxide by π-π stacking with the pyrene of PIL.

Separation of metalloporphyrins from metallation reactions by liquid chromatography and electrophoresis.

PubMed

Duff, G A; Yeager, S A; Singhal, A K; Pestel, B C; Ressner, J M; Foster, N

1987-04-24

The analytical separation of the indium and manganese complexes of three synthetic, meso-substituted, water-soluble porphyrins from their respective free bases in metallation reaction mixtures is described. The ligands tetra-3N-methylpyridyl porphyrin, tetra-4N-methylpyridyl porphyrin and tetra-N,N,N-trimethylanilinium porphyrin are complexed with In (III) and Mn (III) and are separated from residual free base by high-performance liquid chromatography (HPLC) in acidic conditions with gradient elution on ODS bonded stationary phase. Electrophoretic separation is achieved on both cellulose polyacetate strips and polyacrylamide tube gels under basic conditions. Although analytical separations can be achieved by both HPLC and electrophoresis, only HPLC is suitable for the development of preparative scale separations. Column chromatography, ion-pairing and ion-suppression HPLC techniques fail to separate such highly charged and closely related aromatic compounds.

Recovery of hydrogen iodide

DOEpatents

Norman, John H.

1983-01-01

A method of extraction of HI from an aqueous solution of HI and I.sub.2. HBr is added to create a two-phase liquid mixture wherein a dry phase consists essentially of HBr, I and HI and is in equilibrium with a wet phase having a far greater HBr:HI ratio. Using a countercurrent extractor, two solutions can be obtained: a dry HBr--HI--I.sub.2 solution and a wet essentially HBr solution. The dry and wet phases are easily separable, and HI is recovered from the dry phase, after first separating I.sub.2, as by distillation. Alternatively, the HI-HBr liquid mixture is treated to catalytically decompose the HI. HBr is recovered from the wet phase by suitable treatment, including high-pressure distillation, to produce an H.sub.2 O--HBr azeotrope that is not more than 25 mole percent HBr. The azeotrope may be returned for use in an earlier step in the overall process which results in the production of the aqueous solution of HI and I.sub.2 without major detriment because of the presence of HBr.

Recovery of hydrogen iodide

DOEpatents

Norman, J.H.

1983-08-02

A method is described for extraction of HI from an aqueous solution of HI and I[sub 2]. HBr is added to create a two-phase liquid mixture wherein a dry phase consists essentially of HBr, I and HI and is in equilibrium with a wet phase having a far greater HBr:HI ratio. Using a countercurrent extractor, two solutions can be obtained: a dry HBr--HI--I[sub 2] solution and a wet essentially HBr solution. The dry and wet phases are easily separable, and HI is recovered from the dry phase, after first separating I[sub 2], as by distillation. Alternatively, the HI-HBr liquid mixture is treated to catalytically decompose the HI. HBr is recovered from the wet phase by suitable treatment, including high-pressure distillation, to produce an H[sub 2]O--HBr azeotrope that is not more than 25 mole percent HBr. The azeotrope may be returned for use in an earlier step in the overall process which results in the production of the aqueous solution of HI and I[sub 2] without major detriment because of the presence of HBr. 1 fig.

Hybrid carbon nanoparticles modified core-shell silica: a high efficiency carbon-based phase for hydrophilic interaction liquid chromatography.

PubMed

Ibrahim, Mohammed E A; Wahab, M Farooq; Lucy, Charles A

2014-04-11

Hydrophilic interaction liquid chromatography (HILIC) is a fast growing separation technique for hydrophilic and polar analytes. In this work, we combine the unique selectivity of carbon surfaces with the high efficiency of core-shell silica. First, 5 μm core-shell silica is electrostatically coated with 105 nm cationic latex bearing quaternary ammonium groups. Then 50 nm anionic carbon nanoparticles are anchored onto the surface of the latex coated core-shell silica particles to produce a hybrid carbon-silica phase. The hybrid phase shows different selectivity than ten previously classified HILIC column chemistries and 36 stationary phases. The hybrid HILIC phase has shape selectivity for positional isomeric pairs (phthalic/isophthalic and 1-naphthoic/2-naphthoic acids). Fast and high efficiency HILIC separations of biologically important carboxylates, phenols and pharmaceuticals are reported with efficiencies up to 85,000 plates m(-1). Reduced plate height of 1.9 (95,000 plates m(-1)) can be achieved. The hybrid phase is stable for at least 3 months of usage and storage under typical HILIC eluents. Copyright © 2014 Elsevier B.V. All rights reserved.

Process for analyzing CO[sub 2] in air and in water

DOEpatents

Atwater, J.E.; Akse, J.R.; DeHart, J.

1999-06-08

The process of this invention comprises providing a membrane for separating CO[sub 2] into a first CO[sub 2] sample phase and a second CO[sub 2] analyte phase. CO[sub 2] is then transported through the membrane thereby separating the CO[sub 2] with the membrane into a first CO[sub 2] sample phase and a second CO[sub 2] analyte liquid phase including an ionized, conductive, dissociated CO[sub 2] species. Next, the concentration of the ionized, conductive, dissociated CO[sub 2] species in the second CO[sub 2] analyte liquid phase is chemically amplified using a water-soluble chemical reagent which reversibly reacts with undissociated CO[sub 2] to produce conductivity changes therein corresponding to fluctuations in the partial pressure of CO[sub 2] in the first CO[sub 2] sample phase. Finally, the chemically amplified, ionized, conductive, dissociated CO[sub 2] species is introduced to a conductivity measuring instrument. Conductivity changes in the chemically amplified, ionized, conductive, dissociated CO[sub 2] species are detected using the conductivity measuring instrument. 43 figs.

Process for analyzing CO.sub.2 in air and in water

DOEpatents

Atwater, James E.; Akse, James R.; DeHart, Jeffrey

1999-01-01

The process of this invention comprises providing a membrane for separating CO.sub.2 into a first CO.sub.2 sample phase and a second CO.sub.2 analyte phase. CO.sub.2 is then transported through the membrane thereby separating the CO.sub.2 with the membrane into a first CO.sub.2 sample phase and a second CO.sub.2 analyte liquid phase including an ionized, conductive, dissociated CO.sub.2 species. Next, the concentration of the ionized, conductive, dissociated CO.sub.2 species in the second CO.sub.2 analyte liquid phase is chemically amplified using a water-soluble chemical reagent which reversibly reacts with undissociated CO.sub.2 to produce conductivity changes therein corresponding to fluctuations in the partial pressure of CO.sub.2 in the first CO.sub.2 sample phase. Finally, the chemically amplified, ionized, conductive, dissociated CO.sub.2 species is introduced to a conductivity measuring instrument. Conductivity changes in the chemically amplified, ionized, conductive, dissociated CO.sub.2 species are detected using the conductivity measuring instrument.

Process for analyzing CO{sub 2} in seawater

DOEpatents

Atwater, J.E.; Akse, J.R.; DeHart, J.

1997-07-01

The process of this invention comprises providing a membrane for separating CO{sub 2} into a first CO{sub 2} sample phase and a second CO{sub 2} analyte phase. CO{sub 2} is then transported through the membrane thereby separating the CO{sub 2} with the membrane into a first CO{sub 2} sample phase and a second CO{sub 2} analyte liquid phase including an ionized, conductive, dissociated CO{sub 2} species. Next, the concentration of the ionized, conductive, dissociated CO{sub 2} species in the second CO{sub 2} analyte liquid phase is chemically amplified using a water-soluble chemical reagent which reversibly reacts with undissociated CO{sub 2} to produce conductivity changes therein corresponding to fluctuations in the partial pressure of CO{sub 2} in the first CO{sub 2} sample phase. Finally, the chemically amplified, ionized, conductive, dissociated CO{sub 2} species is introduced to a conductivity measuring instrument. Conductivity changes in the chemically amplified, ionized, conductive, dissociated CO{sub 2} species are detected using the conductivity measuring instrument. 43 figs.

Chiral organosilica particles and their use as inducers of conformational deracemization of liquid crystal phases

NASA Astrophysics Data System (ADS)

Cohen, Orit; Ferris, Andrew J.; Adkins, Raymond; Lemieux, Robert P.; Avnir, David; Gelman, Dmitri; Rosenblatt, Charles

2018-03-01

Chiral organosilica particles of size ∼200 nm were synthesized from an enantio-pure multi-armed chiral D-maltose organosilane precursor in the absence of co-condensation with an achiral monomer. Two distinct experiments were performed to demonstrate the particles' ability to induce conformational deracemization of a host liquid crystal. The first involves an electric field-induced tilt of the liquid crystal director in the deracemized smectic-A phase. The other involves domain wall curvature separating left- and right-handed liquid crystal helical pitch domains imposed by the cells' substrates. The results demonstrate unequivocally that enantio-pure organosilica nanoparticles can be synthesized and can induce chirality in a host.

Membrane contactor assisted extraction/reaction process employing ionic liquids

DOEpatents

Lin, Yupo J [Naperville, IL; Snyder, Seth W [Lincolnwood, IL

2012-02-07

The present invention relates to a functionalized membrane contactor extraction/reaction system and method for extracting target species from multi-phase solutions utilizing ionic liquids. One preferred embodiment of the invented method and system relates to an extraction/reaction system wherein the ionic liquid extraction solutions act as both extraction solutions and reaction mediums, and allow simultaneous separation/reactions not possible with prior art technology.

[Anomalous Properties of Water and Aqueous Solutions at Low Temperatures].

PubMed

Matsumoto, Masakazu

2015-01-01

Water has many anomalous properties below the room temperature. The temperature range overlaps with that of the Earth's atmosphere and also with that natural life forms favor. We review the origin of the anomalous properties of water and aqueous solutions in association with the hypothetical second critical point and liquid-liquid phase separation of water hidden in the supercooled state of liquid water.

[Separation and identification of bovine lactoferricin by high performance liquid chromatography-matrix-assisted laser desorption/ionization time of flight/ time of flight mass spectrometry].

PubMed

An, Meichen; Liu, Ning

2010-02-01

A high performance liquid chromatography-matrix-assisted laser desorption/ionization time of flight/time of flight mass spectrometry (HPLC-MALDI-TOF/TOF MS) method was developed for the separation and identification of bovine lactoferricin (LfcinB). Bovine lactoferrin was hydrolyzed by pepsin and then separated by ion exchange chromatography and reversed-phase liquid chromatography (RP-LC). The antibacterial activities of the fractions from RP-LC separation were determined and the protein concentration of the fraction with the highest activity was measured, whose sequence was indentified by MALDI-TOF/TOF MS. The relative molecular mass of LfcinB was 3 124.89 and the protein concentration was 18.20 microg/mL. The method of producing LfcinB proposed in this study has fast speed, high accuracy and high resolution.

Raman spectral evidence of methyl rotation in liquid toluene.

PubMed

Kapitán, Josef; Hecht, Lutz; Bour, Petr

2008-02-21

In order to rationalize subtle details in the liquid phase toluene Raman backscattering spectra, an analysis was performed based on a quantum-mechanical Hamiltonian operator comprising rotation of the methyl group and the angular dependence of vibrational frequencies and polarizability derivatives. The separation of the methyl torsion from the other vibrational motions appears to be necessary in order to explain relative intensity ratios of several bands and an anomalous broadening of spectral intensity observed at 1440 cm(-1). These results suggest that the CH3 group in the liquid phase rotates almost freely, similarly as in the gaseous phase, and that the molecule consequently exhibits effectively C(2v) point group symmetry. A classical description and an adiabatic separation of the methyl rotation from other molecular motion previously used in peptide models is not applicable to toluene because of a strong coupling with other vibrational motions. Density functional computations, particularly the BPW91 functional, provide reasonable estimates of harmonic frequencies and spectral intensities, as well as qualitatively correct fourth-order anharmonic corrections to the vibrational potential.

Miscibility Studies on Polymer Blends Modified with Phytochemicals

NASA Astrophysics Data System (ADS)

Chandrasekaran, Neelakandan; Kyu, Thein

2009-03-01

The miscibility studies related to an amorphous poly(amide)/poly(vinyl pyrrolidone) [PA/PVP] blend with a crystalline phytochemical called ``Mangiferin'' is presented. Phytochemicals are plant derived chemicals which intrinsically possess multiple salubrious properties that are associated with prevention of diseases such as cancer, diabetes, cardiovascular disease, and hypertension. Incorporation of phytochemicals into polymers has shown to have very promising applications in wound healing, drug delivery, etc. The morphology of these materials is crucial to applications like hemodialysis, which is governed by thermodynamics and kinetics of the phase separation process. Hence, miscibility studies of PA/PVP blends with and without mangiferin have been carried out using dimethyl sulfoxide as a common solvent. Differential scanning calorimetry studies revealed that the binary PA/PVP blends were completely miscible at all compositions. However, the addition of mangiferin has led to liquid-liquid phase separation and liquid-solid phase transition in a composition dependent manner. Fourier transformed infrared spectroscopy was undertaken to determine specific interaction between the polymer constituents and the role of possible hydrogen bonding among three constituents will be discussed.

Liquid-liquid and solid-phase extractions of phenols from virgin olive oil and their separation by chromatographic and electrophoretic methods.

PubMed

Bendini, Alessandra; Bonoli, Matteo; Cerretani, Lorenzo; Biguzzi, Barbara; Lercker, Giovanni; Toschi, Tullia Gallina

2003-01-24

The high oxidative stability of virgin olive oil is related to its high monounsaturated/polyunsaturated ratio and to the presence of antioxidant compounds, such as tocopherols and phenols. In this paper, the isolation of phenolic compounds from virgin olive oil, by different methods, was tested and discussed. Particularly liquid-liquid and solid-phase extraction methods were compared, assaying, for the latter, three stationary phases (C8, C18 and Diol) and several elution mixtures. Quantification of phenolic and o-diphenolic substances in the extracts was performed by the traditional Folin-Ciocalteau method and the sodium molybdate reaction, respectively. Furthermore, the quantification of phenolic compounds in the extracts and in a standard mixture was carried out both with diode array and mass spectrometric detection and capillary zone electrophoresis.

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.

Chiral ligand-exchange high-performance liquid chromatography with copper (II)-L-phenylalanine complexes for separation of 3,4-dimethoxy-α-methylphenylalanine racemes.

PubMed

Jia, Dong-Xu; Ai, Zheng-Gui; Xue, Ya-Ping; Zheng, Yu-Guo

2014-11-01

L-3, 4-dimethoxy-α-methylphenylalanine (L-DMMD) is an important intermediate for the synthesis of 3-hydroxy-α-methyl-L-tyrosine (L-methyldopa). This paper describes an efficient, accurate, and low-priced method of high-performance liquid chromatography (HPLC) using chiral mobile phase and conventional C18 column to separate L-DMMD from its enantiomers. The effects of ligands, copper salts, organic modifiers, pHs of mobile phase, and temperatures on the retention factors (k') and selectivity (α) were evaluated to achieve optimal separation performance. Then, thermal analysis of the optimal separation conditions was investigated as well. It was confirmed that the optimal mobile phase was composed of 20 % (v/v) methanol, 8 mM L-phenylalanine (L-Phe), and 4 mM cupric sulfate in water of pH 3.2, and the column temperature was set at 20 °C. Baseline separation of two enantiomers could be obtained through the conventional C18 column with a resolution (R) of 3.18 in less than 18 min. Thermodynamic data (∆∆H and ∆∆S) obtained by Van't Hoff plots revealed the chiral separation was an enthalpy-controlled process. To the best of our knowledge, this is the first report regarding the enantioseparation of DMMD by chiral ligand-exchange HPLC.

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 and characterization of chemical constituents in Ginkgo biloba extract by off-line hydrophilic interaction×reversed-phase two-dimensional liquid chromatography coupled with quadrupole-time of flight mass spectrometry.

PubMed

Ji, Shuai; He, Dan-Dan; Wang, Tian-Yun; Han, Jie; Li, Zheng; Du, Yan; Zou, Jia-Hui; Guo, Meng-Zhe; Tang, Dao-Quan

2017-11-30

Ginkgo biloba extract (GBE), derived from the leaves of Ginkgo biloba L., is one of the most widely used traditional Chinese medicines worldwide. Due to high structural diversity and low abundance of chemical constituents in GBE, conventional reversed-phase liquid chromatography has limited power to meet the needs of its quality control. In this study, an off-line hydrophilic interaction×reversed-phase two-dimensional liquid chromatography (HILIC×RP 2D-LC) system coupled with diode array detection (DAD) and quadrupole time-of-flight mass spectrometry (qTOF-MS) was established to comprehensively analyze the chemical constituents of GBE. After optimizing the chromatographic columns and mobile phase of 2D-LC, a Waters XBridge Amide column using acetonitrile/water/formic acid as the mobile phase was selected as the first dimension to fractionate GBE, and the obtained fractions were further separated on an Agilent Zorbax XDB-C18 column with methanol/water/formic acid as the mobile phase. As a result, a total of 125 compounds were detected in GBE. The orthogonality of the 2D-LC system was 69.5%, and the practical peak capacity was 3864 and 2994, respectively, calculated by two different methods. The structures of 104 compounds were tentatively characterized by qTOF-MS analysis, and 21 of them were further confirmed by comparing with reference standards. This established HILIC×RP 2D-LC-qTOF/MS system can greatly improve the separation and characterization of natural products in GBE or other complicated herbal extracts. Copyright © 2017 Elsevier B.V. All rights reserved.

Investigation of Dispersed and Dispersed Annular (rivulet or Thin Film) Flow Phase Separation in Tees.

NASA Astrophysics Data System (ADS)

McCreery, Glenn Ernest

An experimental and analytical investigation of dispersed and dispersed-annular (rivulet or thin film) flow phase separation in tees has been successfully completed. The research was directed at, but is not specific to, determining flow conditions, following a loss of coolant accident, in the large rectangular passageways leading to vacuum buildings in the containment envelope of some CANDU nuclear reactors. The primary objectives of the research were to: (1) obtain experimental data to help formulate and test mechanistic analytical models of phase separation, and (2) develop the analytical models in computer programs which predict phase separation from upstream flow and pressure conditions and downstream and side branch pressure boundary conditions. To meet these objectives an air-water experimental apparatus was constructed, and consists of large air blowers attached to a long rectangular duct leading to a tee in the horizontal plane. A variety of phenomena was investigated including, for comparison with computer predictions, air streamlines and eddy boundary geometry, drop size spectra, macroscopic mass balances, liquid rivulet pathlines, and trajectories of drops of known size and velocity. Four separate computer programs were developed to analyze phase separation. Three of the programs are used sequentially to calculate dispersed mist phase separation in a tee. The fourth is used to calculate rivulet or thin film pathlines. Macroscopic mass balances are calculated from a summation of mass balances for drops with representative sizes (and masses) spaced across the drop size spectrum. The programs are tested against experimental data, and accurately predict gas flow fields, drop trajectories, rivulet pathlines and macroscopic mass balances. In addition to development of the computer programs, analysis was performed to specify the scaling of dispersed mist and rivulet or thin film flow, to investigate pressure losses in tees, and the inter-relationship of loss coefficients, contraction coefficients, and eddy geometry. The important transient effects of liquid storage in eddies were also analyzed.

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

Two-component Gaussian core model: Strong-coupling limit, Bjerrum pairs, and gas-liquid phase transition.

PubMed

Frydel, Derek; Levin, Yan

2018-01-14

In the present work, we investigate a gas-liquid transition in a two-component Gaussian core model, where particles of the same species repel and those of different species attract. Unlike a similar transition in a one-component system with particles having attractive interactions at long separations and repulsive interactions at short separations, a transition in the two-component system is not driven solely by interactions but by a specific feature of the interactions, the correlations. This leads to extremely low critical temperature, as correlations are dominant in the strong-coupling limit. By carrying out various approximations based on standard liquid-state methods, we show that a gas-liquid transition of the two-component system poses a challenging theoretical problem.

Two-component Gaussian core model: Strong-coupling limit, Bjerrum pairs, and gas-liquid phase transition

NASA Astrophysics Data System (ADS)

Frydel, Derek; Levin, Yan

2018-01-01

In the present work, we investigate a gas-liquid transition in a two-component Gaussian core model, where particles of the same species repel and those of different species attract. Unlike a similar transition in a one-component system with particles having attractive interactions at long separations and repulsive interactions at short separations, a transition in the two-component system is not driven solely by interactions but by a specific feature of the interactions, the correlations. This leads to extremely low critical temperature, as correlations are dominant in the strong-coupling limit. By carrying out various approximations based on standard liquid-state methods, we show that a gas-liquid transition of the two-component system poses a challenging theoretical problem.

U-shaped, double-tapered, fiber-optic sensor for effective biofilm growth monitoring.

PubMed

Zhong, Nianbing; Zhao, Mingfu; Li, Yishan

2016-02-01

To monitor biofilm growth on polydimethylsiloxane in a photobioreactor effectively, the biofilm cells and liquids were separated and measured using a sensor with two U-shaped, double-tapered, fiber-optic probes (Sen. and Ref. probes). The probes' Au-coated hemispherical tips enabled double-pass evanescent field absorption. The Sen. probe sensed the cells and liquids inside the biofilm. The polyimide-silica hybrid-film-coated Ref. probe separated the liquids from the biofilm cells and analyzed the liquid concentration. The biofilm structure and active biomass were also examined to confirm the effectiveness of the measurement using a simulation model. The sensor was found to effectively respond to the biofilm growth in the adsorption through exponential phases at thicknesses of 0-536 μm.

Single-reactor process for producing liquid-phase organic compounds from biomass

DOEpatents

Dumesic, James A.; Simonetti, Dante A.; Kunkes, Edward L.

2015-12-08

Disclosed is a method for preparing liquid fuel and chemical intermediates from biomass-derived oxygenated hydrocarbons. The method includes the steps of reacting in a single reactor an aqueous solution of a biomass-derived, water-soluble oxygenated hydrocarbon reactant, in the presence of a catalyst comprising a metal selected from the group consisting of Cr, Mn, Fe, Co, Ni, Cu, Mo, Tc, Ru, Rh, Pd, Ag, W, Re, Os, Ir, Pt, and Au, at a temperature, and a pressure, and for a time sufficient to yield a self-separating, three-phase product stream comprising a vapor phase, an organic phase containing linear and/or cyclic mono-oxygenated hydrocarbons, and an aqueous phase.

Single-reactor process for producing liquid-phase organic compounds from biomass

DOEpatents

Dumesic, James A [Verona, WI; Simonetti, Dante A [Middleton, WI; Kunkes, Edward L [Madison, WI

2011-12-13

Disclosed is a method for preparing liquid fuel and chemical intermediates from biomass-derived oxygenated hydrocarbons. The method includes the steps of reacting in a single reactor an aqueous solution of a biomass-derived, water-soluble oxygenated hydrocarbon reactant, in the presence of a catalyst comprising a metal selected from the group consisting of Cr, Mn, Fe, Co, Ni, Cu, Mo, Tc, Ru, Rh, Pd, Ag, W, Re, Os, Ir, Pt, and Au, at a temperature, and a pressure, and for a time sufficient to yield a self-separating, three-phase product stream comprising a vapor phase, an organic phase containing linear and/or cyclic mono-oxygenated hydrocarbons, and an aqueous phase.

High-performance liquid chromatography separation and intact mass analysis of detergent-solubilized integral membrane proteins

PubMed Central

Berridge, Georgina; Chalk, Rod; D’Avanzo, Nazzareno; Dong, Liang; Doyle, Declan; Kim, Jung-In; Xia, Xiaobing; Burgess-Brown, Nicola; deRiso, Antonio; Carpenter, Elisabeth Paula; Gileadi, Opher

2011-01-01

We have developed a method for intact mass analysis of detergent-solubilized and purified integral membrane proteins using liquid chromatography–mass spectrometry (LC–MS) with methanol as the organic mobile phase. Membrane proteins and detergents are separated chromatographically during the isocratic stage of the gradient profile from a 150-mm C3 reversed-phase column. The mass accuracy is comparable to standard methods employed for soluble proteins; the sensitivity is 10-fold lower, requiring 0.2–5 μg of protein. The method is also compatible with our standard LC–MS method used for intact mass analysis of soluble proteins and may therefore be applied on a multiuser instrument or in a high-throughput environment. PMID:21093405

Simulating compressible-incompressible two-phase flows

NASA Astrophysics Data System (ADS)

Denner, Fabian; van Wachem, Berend

2017-11-01

Simulating compressible gas-liquid flows, e.g. air-water flows, presents considerable numerical issues and requires substantial computational resources, particularly because of the stiff equation of state for the liquid and the different Mach number regimes. Treating the liquid phase (low Mach number) as incompressible, yet concurrently considering the gas phase (high Mach number) as compressible, can improve the computational performance of such simulations significantly without sacrificing important physical mechanisms. A pressure-based algorithm for the simulation of two-phase flows is presented, in which a compressible and an incompressible fluid are separated by a sharp interface. The algorithm is based on a coupled finite-volume framework, discretised in conservative form, with a compressive VOF method to represent the interface. The bulk phases are coupled via a novel acoustically-conservative interface discretisation method that retains the acoustic properties of the compressible phase and does not require a Riemann solver. Representative test cases are presented to scrutinize the proposed algorithm, including the reflection of acoustic waves at the compressible-incompressible interface, shock-drop interaction and gas-liquid flows with surface tension. Financial support from the EPSRC (Grant EP/M021556/1) is gratefully acknowledged.

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

Aniline-modified porous graphitic carbon for hydrophilic interaction and attenuated reverse phase liquid chromatography.

PubMed

Iverson, Chad D; Lucy, Charles A

2014-12-19

Most stationary phases for hydrophilic interaction liquid chromatography (HILIC) and reversed phase liquid chromatography (RPLC) are based on silica. Porous graphitic carbon (PGC) is an attractive alternative to silica-based phases due to its chemical and thermal stability, and unique selectivity. However, native PGC is strongly hydrophobic and in some instances excessively retentive. PGC particles with covalently attached aniline groups (Dimethylaniline-PGC and Aniline-PGC) were synthesized to alter the surface polarity of PGC. First, the diazonium salt of N,N-dimethyl-p-phenylenediamine or 4-nitroaniline was adsorbed onto the PGC surface. The adsorbed salt was reduced with sodium borohydride and (Aniline-PGC only) the nitro group was further reduced with iron powder to the aniline. X-ray photoelectron spectroscopy confirmed the surface functionalities and that these moieties were introduced to the surface at concentrations of 0.9 and 2.1molecules/nm(2), respectively. These modified PGC phases (especially Aniline-PGC) were evaluated as HILIC and reversed phases. The Dimethylaniline-PGC phase displayed only weak HILIC retention of phenolic solutes. In contrast, the Aniline-PGC phase displayed up to nearly a 7-fold increase in HILIC retention vs. an aniline-silica phase and selectivity that differed from 10 other HILIC phases. Introduction of aniline groups to the PGC surface reduced the RPLC retentivity of PGC up to more than 5-fold and improved the separation efficiency up to 6-fold. The chromatographic performance of Aniline-PGC is demonstrated by separations of nucleotides, nucleosides, carboxylic acids, basic pharmaceuticals, and other compounds. Copyright © 2014 Elsevier B.V. All rights reserved.

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.

Characterization of rhamnolipids by liquid chromatography/mass spectrometry after solid-phase extraction.

PubMed

Behrens, Beate; Engelen, Jeannine; Tiso, Till; Blank, Lars Mathias; Hayen, Heiko

2016-04-01

Rhamnolipids are surface-active agents with a broad application potential that are produced in complex mixtures by bacteria of the genus Pseudomonas. Analysis from fermentation broth is often characterized by laborious sample preparation and requires hyphenated analytical techniques like liquid chromatography coupled to mass spectrometry (LC-MS) to obtain detailed information about sample composition. In this study, an analytical procedure based on chromatographic method development and characterization of rhamnolipid sample material by LC-MS as well as a comparison of two sample preparation methods, i.e., liquid-liquid extraction and solid-phase extraction, is presented. Efficient separation was achieved under reversed-phase conditions using a mixed propylphenyl and octadecylsilyl-modified silica gel stationary phase. LC-MS/MS analysis of a supernatant from Pseudomonas putida strain KT2440 pVLT33_rhlABC grown on glucose as sole carbon source and purified by solid-phase extraction revealed a total of 20 congeners of di-rhamnolipids, mono-rhamnolipids, and their biosynthetic precursors 3-(3-hydroxyalkanoyloxy)alkanoic acids (HAAs) with different carbon chain lengths from C8 to C14, including three rhamnolipids with uncommon C9 and C11 fatty acid residues. LC-MS and the orcinol assay were used to evaluate the developed solid-phase extraction method in comparison with the established liquid-liquid extraction. Solid-phase extraction exhibited higher yields and reproducibility as well as lower experimental effort.

Tests of a 2-Stage, Axial-Flow, 2-Phase Turbine

NASA Technical Reports Server (NTRS)

Elliott, D. G.

1982-01-01

A two phase flow turbine with two stages of axial flow impulse rotors was tested with three different working fluid mixtures at a shaft power of 30 kW. The turbine efficiency was 0.55 with nitrogen and water of 0.02 quality and 94 m/s velocity, 0.57 with Refrigerant 22 of 0.27 quality and 123 m/s velocity, and 0.30 with steam and water of 0.27 quality and 457 m/s velocity. The efficiencies with nitrogen and water and Refrigerant 22 were 86 percent of theoretical. At that fraction of theoretical, the efficiencies of optimized two phase turbines would be in the low 60 percent range with organic working fluids and in the mid 50 percent range with steam and water. The recommended turbine design is a two stage axial flow impulse turbine followed by a rotary separator for discharge of separate liquid and gas streams and recovery of liquid pressure.

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.

[Simultaneous determination of 15 industrial synthetic dyes in condiment by solid phase extraction-high performance liquid chromatography].

PubMed

Liu, Min; Li, Xiaolin; Bie, Wei; Wang, Minglin; Feng, Qian

2011-02-01

A new method was established for the determination of 15 industrial synthetic dyes in condiment by solid phase extraction-high performance liquid chromatography (SPE-HPLC). The samples were extracted by methanol-water (1:1, v/v) and purified by a solid phase extraction column. Then, the chromatographic separation was achieved on a Luna C18 column by linear gradient elution. The mobile phase was 10 mmol/L ammonium acetate-acetonitrile (containing 1% acetic acid). The results showed that the 15 industrial synthetic dyes can be separated efficiently. The recoveries of the 15 industrial synthetic dyes spiked in condiment were between 84.6% and 114.2% with the relative standard deviations of 0.9% - 10.3%. The limits of detection of this method was 0.05 - 0.18 mg/kg for the 15 industrial synthetic dyes. The method is simple, sensitive, accurate, repeatable and can be used for simultaneous determination of the 15 illegally added industrial synthetic dyes.

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

PubMed

Englert, Michael; Vetter, Walter

2014-05-16

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

Ionic liquid-modified materials for solid-phase extraction and separation: a review.

PubMed

Vidal, Lorena; Riekkola, Marja-Liisa; Canals, Antonio

2012-02-17

In recent years, materials science has propelled to the research forefront. Ionic liquids with unique and fascinating properties have also left their footprints to the developments of materials science during the last years. In this review we highlight some of their recent advances and provide an overview at the current status of ionic liquid-modified materials applied in solid-phase extraction, liquid and gas chromatography and capillary electrochromatography with reference to recent applications. In addition, the potential of ionic liquids in the modification of capillary inner wall in capillary electrophoresis is demonstrated. The main target material modified with ionic liquids is silica, but polymers and monoliths have recently joined the studies. Although imidazolium is still clearly the most commonly used ionic liquid for the covalently modification of materials, the exploitation of pyridinium and phosphonium will most probably increase in the future. Copyright © 2011 Elsevier B.V. All rights reserved.

Physicochemical processes in embryonic plant tissue during the transition to the state of cold anabiosis and storage at liquid nitrogen temperature

NASA Astrophysics Data System (ADS)

Khodko, A. T.; Lysak, Yu. S.

2017-10-01

Critical opalescence phenomenon was observed in the cytoplasm of garlic embryonic tissue—meristem—upon cooling in liquid nitrogen vapor, indicating liquid-liquid phase transition in the system. It was established that cells of the meristem tissue survive the cooling-thawing cycle. We suggest that the transition of meristem tissue to the state of anabiosis is mainly due to a drastic slowing of the diffusion in the cytoplasm caused by the passage of the solution through the critical point, followed by the formation of a dispersed system—a highly concentrated emulsion—as a result of a liquid-liquid phase transition. This macrophase separation is characteristic of polymer-solvent systems. We established the regime of cooling down to liquid nitrogen temperature and subsequent thawing in the cryopreservation cycle for the biological object under study, which ensures the preservation of tissue viability.

Amphiphilic phase-transforming catalysts for transesterification of triglycerides

NASA Astrophysics Data System (ADS)

Nawaratna, Gayan Ivantha

Heterogeneous catalytic reactions that involve immiscible liquid-phase reactants are challenging to conduct due to limitations associated with mass transport. Nevertheless, there are numerous reactions such as esterification, transesterification, etherification, and hydrolysis where two immiscible liquid reactants (such as polar and non-polar liquids) need to be brought into contact with a catalyst. With the intention of alleviating mass transport issues associated with such systems but affording the ability to separate the catalyst once the reaction is complete, the overall goal of this study is geared toward developing a catalyst that has emulsification properties as well as the ability to phase-transfer (from liquid-phase to solid-phase) while the reaction is ongoing and evaluating the effectiveness of such a catalytic process in a practical reaction. To elucidate this concept, the transesterification reaction was selected. Metal-alkoxides that possess acidic and basic properties (to catalyze the reaction), amphiphilic properties (to stabilize the alcohol/oil emulsion) and that can undergo condensation polymerization when heated (to separate as a solid subsequent to the completion of the reaction) were used to test the concept. Studies included elucidating the effect of metal sites and alkoxide sites and their concentration effects on transesterification reaction, effect of various metal alkoxide groups on the phase stability of the reactant system, and kinetic effects of the reaction system. The studies revealed that several transition-metal alkoxides, especially, titanium and yttrium based, responded positively to this reaction system. These alkoxides were able to be added to the reaction medium in liquid phase and were able to stabilize the alcohol/oil system. The alkoxides were selective to the transesterification reaction giving a range of ester yields (depending on the catalyst used). It was also observed that transition-metal alkoxides were able to be recovered in the form of their polymerized counterparts as a result of condensation polymerization subsequent to completion of the transesterification reaction.

Transverse injection of a particle-laden liquid jet in supersonic flow: A three-phase flow

NASA Technical Reports Server (NTRS)

Schetz, J. A.; Ogg, J. C.

1980-01-01

The results of a two part study of the behavior of particle laden liquid jets injected into air are presented. Water was used as the liquid carrier and either 1-37 or 13-44 microns diam. spherical glass beads with a specific gravity of 2.8-3.0 as the particles. The observations were mainly photographic. The breakup of jets injected into still air was investigated as a function of particle loading, and the results were compared to the pure liquid jet case. The jets were found to be more stable with particles present. The length to breakup was increased, and the formation of satellite droplets was suppressed. The penetration and breakup of transverse jets in a Mach 3.0 air stream was studied. The general breakup mechanism of wave formation was found to be the same as for the all liquid case. Significant separation of the phases was observed, and the penetration of the liquid phase was reduced compared to all liquid cases at the same value of the jet to free stream momentum flux ratio.

Simultaneous quantification of major flavonoids in "Bawanghua", the edible flower of Hylocereus undatus using pressurised liquid extraction and high performance liquid chromatography.

PubMed

Yi, Yan; Zhang, Qing-Wen; Li, Song-Lin; Wang, Ying; Ye, Wen-Cai; Zhao, Jing; Wang, Yi-Tao

2012-11-15

A pressurised liquid extraction (PLE) and high performance liquid chromatography (HPLC) method was developed for simultaneous quantification of six major flavonoids in edible flower of Hylocereus undatus. In order to achieve the baseline separation of two pairs of isomers, the HPLC conditions were optimised with different kind of reversed phase columns and mobile phase gradient programs. In addition, the solvent concentration, extraction temperature, extraction time and flush cycle for PLE were also optimised. Zorbax SB-C8 (100×2.1 mm, 1.8 μm) column was chosen with acetonitrile and water containing 0.1% trifluoroacetic acid as mobile phase, the six analytes were eluted with baseline separation. The calibration curves showed good linearity (r(2)>0.9994) with LODs and LOQs less than 0.90 and 3.60 ng respectively. The RSDs for intra- and inter-day repeatability was not more than 1.09% and 1.79% respectively. The overall recovery of the assay was 96.9-105.2%. The sample was stable for at least 12 h. The newly established method was successfully applied to quantify six flavonoids in different parts of "Bawanghua", and the commercial samples from different locations. Copyright © 2012 Elsevier Ltd. All rights reserved.

Method of forming supported doped palladium containing oxidation catalysts

DOEpatents

Mohajeri, Nahid

2014-04-22

A method of forming a supported oxidation catalyst includes providing a support comprising a metal oxide or a metal salt, and depositing first palladium compound particles and second precious metal group (PMG) metal particles on the support while in a liquid phase including at least one solvent to form mixed metal comprising particles on the support. The PMG metal is not palladium. The mixed metal particles on the support are separated from the liquid phase to provide the supported oxidation catalyst.

Reduced Gravity Gas and Liquid Flows: Simple Data for Complex Problems

NASA Technical Reports Server (NTRS)

McQuillen, John; Motil, Brian

2001-01-01

While there have been many studies for two-phase flow through straight cylindrical tubes, more recently, a new group of studies have emerged that examine two-phase flow through non-straight, non-cylindrical geometries, including expansions, contractions, tees, packed beds and cyclonic separation devices. Although these studies are still, relatively speaking, in their infancy, they have provided valuable information regarding the importance of the flow momentum, and the existence of liquid dryout due to sharp comers in microgravity.

Wetting in a Colloidal Liquid-Gas System

NASA Astrophysics Data System (ADS)

Wijting, W. K.; Besseling, N. A.; Stuart, M. A.

2003-05-01

We present first observations of wetting phenomena in depletion interaction driven, phase separated colloidal dispersions (coated silica cyclohexane-polydimethylsiloxane). The contact angle of the colloidal liquid-gas interface at a solid substrate (coated glass) was determined for a series of compositions. Upon approach to the critical point, a transition occurs from partial to complete wetting.

Wetting in a colloidal liquid-gas system.

PubMed

Wijting, W K; Besseling, N A M; Stuart, M A Cohen

2003-05-16

We present first observations of wetting phenomena in depletion interaction driven, phase separated colloidal dispersions (coated silica-cyclohexane-polydimethylsiloxane). The contact angle of the colloidal liquid-gas interface at a solid substrate (coated glass) was determined for a series of compositions. Upon approach to the critical point, a transition occurs from partial to complete wetting.

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

Blay, J.A.

The problem of the determination of micro-amounts of uranium in aqueous and organic phases in liquid-liquid extraction processes, original ones, and extraction residues was solved by a chromatographic separation of the uranium by means of columns of activated cellulose and further spectrophotometric evaluation using the thiocyanate complex in aqueous medium. The usable range is 5 to 200 mu g.