Analysis of imazaquin in soybeans by solid-phase extraction and high-performance liquid chromatography.

PubMed

Guo, C; Hu, J-Y; Chen, X-Y; Li, J-Z

2008-02-01

An analytical method for the determination imazaquin residues in soybeans was developed. The developed liquid/liquid partition and strong anion exchange solid-phase extraction procedures provide the effective cleanup, removing the greatest number of sample matrix interferences. By optimizing mobile-phase pH water/acetonitrile conditions with phosphoric acid, using a C-18 reverse-phase chromatographic column and employing ultraviolet detection, excellent peak resolution was achieved. The combined cleanup and chromatographic method steps reported herein were sensitive and reliable for determining the imazaquin residues in soybean samples. This method is characterized by recovery >88.4%, precision <6.7% CV, and sensitivity of 0.005 ppm, in agreement with directives for method validation in residue analysis. Imazaquin residues in soybeans were further confirmed by high performance liquid chromatography-mass spectrometry (LC-MS). The proposed method was successfully applied to the analysis of imazaquin residues in soybean samples grown in an experimental field after treatments of imazaquin formulation.

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.

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.

Recent applications of hydrophilic interaction liquid chromatography in pharmaceutical analysis.

PubMed

Zhang, Qian; Yang, Feng-Qing; Ge, Liya; Hu, Yuan-Jia; Xia, Zhi-Ning

2017-01-01

Hydrophilic interaction liquid chromatography, an alternative liquid chromatography mode, is of particular interest in separating hydrophilic and polar ionic compounds. Compared with traditional liquid chromatography techniques, hydrophilic interaction liquid chromatography offers specific advantages mainly including: (1) relatively green and water-soluble mobile phase composition, which enhances the solubility of hydrophilic and polar ionic compounds; (2) no need for ion-pairing reagents and high content of organic solvent, which benefits mass spectrometry detection; (3) high orthogonality to reverse-phase liquid chromatography, well adapted to two-dimensional liquid chromatography for complicated samples. Therefore, hydrophilic interaction liquid chromatography has been rapidly developed in many areas over the past decades. This review summarizes the recent progress (from 2012 to July 2016) of hydrophilic interaction liquid chromatography in pharmaceutical analysis, with the focus on detecting chemical drugs in various matrices, charactering active compounds of natural products and assessing biotherapeutics through typical structure unit. Moreover, the retention mechanism and behavior of analytes in hydrophilic interaction liquid chromatography as well as some novel hydrophilic interaction liquid chromatography columns used for pharmaceutical analysis are also described. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Comparison of core-shell and totally porous ultra high performance liquid chromatographic stationary phases based on their selectivity towards alfuzosin compounds.

PubMed

Szulfer, Jarosław; Plenis, Alina; Bączek, Tomasz

2014-06-13

This paper focuses on the application of a column classification system based on the Katholieke Universiteit Leuven for the characterization of physicochemical properties of core-shell and ultra-high performance liquid chromatographic stationary phases, followed by the verification of the reliability of the obtained column classification in pharmaceutical practice. In the study, 7 stationary phases produced in core-shell technology and 18 ultra-high performance liquid chromatographic columns were chromatographically tested, and ranking lists were built on the FKUL-values calculated against two selected reference columns. In the column performance test, an analysis of alfuzosin in the presence of related substances was carried out using the brands of the stationary phases with the highest ranking positions. Next, a system suitability test as described by the European Pharmacopoeia monograph was performed. Moreover, a study was also performed to achieve a purposeful shortening of the analysis time of the compounds of interest using the selected stationary phases. Finally, it was checked whether methods using core-shell and ultra-high performance liquid chromatographic columns can be an interesting alternative to the high-performance liquid chromatographic method for the analysis of alfuzosin in pharmaceutical practice. Copyright © 2014 Elsevier B.V. All rights reserved.

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.

Aspects of High-Resolution Gas Chromatography as Applied to the Analysis of Hydrocarbon Fuels and Other Complex Organic Mixtures. Volume 2. Survey of Sample Insertion Techniques.

DTIC Science & Technology

1985-06-01

packed column, with low liquid loading (2. 0 mm ID, 4% liquid phase loading on diatomaceous earth *) 0.3 Medium bore analytical packed column, with...moderate liquid loading (4. 5 mm ID, 8%16 liquid phase loading on diatomaceous earth *) 3.0 -3 * diatomaceous earth density 0.24 gm cm 12 associated with the...hydrocarbon fuels. Certain injector inserts have contained packed chromatographic media, e.g., stationary phases coated onto diatomaceous earth . This type

Identification of proteins in a human pleural exudate using two-dimensional preparative liquid-phase electrophoresis and matrix-assisted laser desorption/ionization mass spectrometry.

PubMed

Nilsson, C L; Puchades, M; Westman, A; Blennow, K; Davidsson, P

1999-01-01

Pleural effusion may occur in patients suffering from physical trauma or systemic disorders such as infection, inflammation, or cancer. In order to investigate proteins in a pleural exudate from a patient with severe pneumonia, we used a strategy that combined preparative two-dimensional liquid-phase electrophoresis (2-D LPE), matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS) and Western blotting. Preparative 2-D LPE is based on the same principles as analytical 2-D gel electrophoresis, except that the proteins remain in liquid phase during the entire procedure. In the first dimension, liquid-phase isoelectric focusing allows for the enrichment of proteins in liquid fractions. In the Rotofor cell, large volumes (up to 55 mL) and protein amounts (up to 1-2 g) can be loaded. Several low abundance proteins, cystatin C, haptoglobin, transthyretin, beta2-microglobulin, and transferrin, were detected after liquid-phase isoelectric focusing, through Western blotting analysis, in a pleural exudate (by definition, >25 g/L total protein). Direct MALDI-TOF-MS analysis of proteins in a Rotofor fraction is demonstrated as well. MALDI-TOF-MS analysis of a tryptic digest of a continuous elution sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE) fraction confirmed the presence of cystatin C. By applying 2-D LPE, MALDI-TOF-MS, and Western blotting to the analysis of this pleural exudate, we were able to confirm the identity of proteins of potential diagnostic value. Our findings serve to illustrate the usefulness of this combination of methods in the analysis of pathological fluids.

Hugoniots of aerogels involving carbon and resorcinol formaldehyde

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

Hrubesh, L H; Ree, F H; Schmidt, R D

1999-06-24

Recently, a first-order phase transition is predicted in liquid carbon using atomistic simulation and Brenner's bond order potential. There are also experimental data suggesting a possibility for a first-order phase transition. In light of this, a thermochemical equilibrium code (CHEQ) is used to provide guidance to experiments to find a liquid-liquid phase change in carbon foam and carbon-rich aerogel, resorcinol formaldehyde. Isotherms and Hugoniots were computed based on the previous analysis by van Thiel and Ree. The present calculations predict the liquid-liquid-graphite triple point to be at 5000 K and 5.2 GPa and its critical point to be at 6000more » K and 8.8 GPa. The present Hugoniot calculations suggest that the liquid-liquid phase transition may be detected by performing a shock experiment with initial density of approximately 0.15 gm/cm{sup 3}.« less

Kelvin-Helmholtz instability of a thin liquid sheet: Effect of the gas-boundary layer

NASA Astrophysics Data System (ADS)

Tirumkudulu, Mahesh

2017-11-01

It is well known that when a thin liquid sheet moves with respect to a surrounding gas phase, the liquid sheet is susceptible to the Kelvin-Helmholtz instability. Here, flow in both the liquid and the gas phases are assumed to be inviscid. In this work, we include exactly via a perturbation analysis, the influence of the growing boundary layer in the gas phase in the base flow and show that both temporal and spatial growth rates obtained from the linear stability analysis are significantly reduced due to the presence of the boundary layer. These results are in line with the simulation results of Lozano et al. and Tammisola et al.. We conclude with the implication of these results on the break-up of radially expanding liquid sheets. Funding from IIT Bombay, CSIR India, and Trinity College, Cambridge University is acknowledged.

Solid–Liquid Phase Change Driven by Internal Heat Generation

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

John Crepeau; Ali s. Siahpush

2012-07-01

This article presents results of solid-liquid phase change, the Stefan Problem, where melting is driven internal heat generation, in a cylindrical geometry. The comparison between a quasi-static analytical solution for Stefan numbers less than one and numerical solutions shows good agreement. The computational results of phase change with internal heat generation show how convection cells form in the liquid region. A scale analysis of the same problem shows four distinct regions of the melting process.

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.

The investigation of critical burning of fuel droplets

NASA Technical Reports Server (NTRS)

Allison, C. B.; Canada, G. S.; Faeth, G. M.

1973-01-01

The combustion and evaporation of liquid fuels at high pressures were investigated. Particular emphasis was placed on conditions where the liquid surface approaches the thermodynamic critical point during combustion. The influence of transient effects on a burning liquid fuel was also investigated through both analysis and measurements of the response of liquid monopropellant combustion to imposed pressure oscillations. Work was divided into four phases (1) Droplet combustion at high pressures, which consider both measurement and analysis of the porous sphere burning rate of liquids in a natural convection environment at elevated pressure. (2) High pressure droplet burning in combustion gases, which involved steady burning and evaporation of liquids from porous spheres in a high pressure environment that simulates actual combustion chamber conditions. (3) Liquid strand combustion, which considered the burning rate, the state of the liquid surface and the liquid phase temperature distribution of a burning liquid monopropellant column over a range of pressures. (4) Oscillatory combustion, which was a theoretical and experimental investigation of the response of a burning liquid monopropellant to pressure oscillations.

Highly concentrated, ring-shaped phase conversion laser-induced breakdown spectroscopy technology for liquid sample analysis.

PubMed

Lin, Qingyu; Wei, Zhimei; Guo, Hongli; Wang, Shuai; Guo, Guangmeng; Zhang, Zhi; Duan, Yixiang

2017-06-10

A highly concentrated, ring-shaped phase conversion (RSPC) method was developed for liquid sample analysis using the laser-induced breakdown spectroscopy (LIBS) technique. In this work, test samples were prepared by mixing the metal particles with polyvinyl alcohol (PVA) supporter in liquid phase. With heat, the PVA solution solidified inside a modified glass petri dish, forming a metal-enriched polymer ring film. Distinguished from other traditional liquid-to-solid conversing methods, the proposed new method takes advantage of enhanced homogeneity for the target elements inside the ring film. The modified glass petri dish was used to control the ring-shaped concentration. Due to the specially designed circular groove at the bottom of this dish, where the PVA solution and liquid sample mixture accumulated, the target elements were concentrated in this small ring, which is beneficial for enhancing and stabilizing the plasma signals compared to the direct liquid sample analysis using LIBS. The limits of detection for Ag, Cu, Cr, and Ba obtained with the RSPC-LIBS technology were 0.098  μg·mL -1 , 0.18  μg·mL -1 , 0.83  μg·mL -1 , and 0.046  μg·mL -1 , respectively, which provided greater improvement than the direct bulk liquid analysis using LIBS.

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

Effectiveness of Liquid-Liquid Extraction, Solid Phase Extraction, and Headspace Technique for Determination of Some Volatile Water-Soluble Compounds of Rose Aromatic Water

PubMed Central

2017-01-01

Steam distillation is used to isolate scent of rose flowers. Rose aromatic water is commonly used in European cuisine and aromatherapy besides its use in cosmetic industry for its lovely scent. In this study, three different sampling techniques, liquid-liquid extraction (LLE), headspace technique (HS), and solid phase extraction (SPE), were compared for the analysis of volatile water-soluble compounds in commercial rose aromatic water. Some volatile water-soluble compounds of rose aromatic water were also analyzed by gas chromatography mass spectrometry (GCMS). In any case, it was concluded that one of the solid phase extraction methods led to higher recoveries for 2-phenylethyl alcohol (PEA) in the rose aromatic water than the liquid-liquid extraction and headspace technique. Liquid-liquid extraction method provided higher recovery ratios for citronellol, nerol, and geraniol than others. Ideal linear correlation coefficient values were observed by GCMS for quantitative analysis of volatile compounds (r2 ≥ 0.999). Optimized methods showed acceptable repeatability (RSDs < 5%) and excellent recovery (>95%). For compounds such as α-pinene, linalool, β-caryophyllene, α-humulene, methyl eugenol, and eugenol, the best recovery values were obtained with LLE and SPE. PMID:28791049

High-pressure phase diagrams of liquid CO2 and N2

NASA Astrophysics Data System (ADS)

Boates, Brian; Bonev, Stanimir

2011-06-01

The phase diagrams of liquid CO2 and N2 have been investigated using first-principles theory. Both materials exhibit transitions to conducting liquids at high temperatures (T) and relatively modest pressures (P). Furthermore, both liquids undergo polymerization phase transitions at pressures comparable to their solid counterparts. The liquid phase diagrams have been divided into several regimes through a detailed analysis of changes in bonding, as well as structural and electronic properties for pressures and temperatures up to 200 GPa and 10 000 K, respectively. Similarities and differences between the high- P and T behavior of these fluids will be discussed. Calculations of the Hugoniot are in excellent agreement with available experimental data. Work supported by NSERC, LLNL, and the Killam Trusts. Prepared by LLNL under Contract DE-AC52-07NA27344.

Phase behavior of thermotropic chiral liquid crystal with wide blue phase

NASA Astrophysics Data System (ADS)

Jessy, P. J.; Radha, S.; Nainesh, Patel

2018-04-01

We modified the phase transitions of a thermotropic chiral nematic liquid crystal system with various concentrations of chiral component and investigated their phase behavior and optical properties. The study shows that coupling between chirality and nematicity of liquid crystals lead to changes in phase morphology with extended temperature window of blue phase including human body temperatures and enhanced thermochromism performance. The temperature dependent refractive index analysis in the visible spectral region reveals that the optical modulation due to pitch variation of helical pattern results in the creation of new mesophases and more pronounced chirality in mixtures leading to blue phase which can be controlled by the chiral concentration. The appearance of extended blue phases with primary colors will pave way for the development of new photonic devices.

Recovery of Picloram and 2,4-Dichlorophenoxyacetic Acid from Aqueous Samples by Reversed-Phase Solid-Phase Extraction

Treesearch

Martha J.M. Wells; Jerry L. Michael

1987-01-01

Extensive preparation of samples before chromatographic analysis is usually the most time-consuming process in the determination of many organic compounds in environmental matrices. In the past, removal of some organic from aqueous solution was commonly done by liquid/liquid extraction. However, the introduction of stable, covalently bonded reversed-phase sorbents now...

Compiled visualization with IPI method for analysing of liquid liquid mixing process

NASA Astrophysics Data System (ADS)

Jasikova, Darina; Kotek, Michal; Kysela, Bohus; Sulc, Radek; Kopecky, Vaclav

2018-06-01

The article deals with the research of mixing process using visualization techniques and IPI method. Characteristics of the size distribution and the evolution of two liquid-liquid phase's disintegration were studied. A methodology has been proposed for visualization and image analysis of data acquired during the initial phase of the mixing process. IPI method was used for subsequent detailed study of the disintegrated droplets. The article describes advantages of usage of appropriate method, presents the limits of each method, and compares them.

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.

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...

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...

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.

Detection and Identification: Instrumentation and Calibration for Air/Liquid/Surface-borne Nanoscale Particles

NASA Astrophysics Data System (ADS)

Ling, Tsz Yan; Zuo, Zhili; Pui, David Y. H.

2013-04-01

Nanoscale particles can be found in the air-borne, liquid-borne and surface-borne dispersed phases. Measurement techniques for nanoscale particles in all three dispersed phases are needed for the environmental, health and safety studies of nanomaterials. We present our studies on connecting the nanoparticle measurements in different phases to enhance the characterization capability. Microscopy analysis for particle morphology can be performed by depositing air-borne or liquid-borne nanoparticles on surfaces. Detection limit and measurement resolution of the liquid-borne nanoparticles can be enhanced by aerosolizing them and taking advantage of the well-developed air-borne particle analyzers. Sampling electrically classified air-borne virus particles with a gelatin filter provides higher collection efficiency than a liquid impinger.

Extraterrestrial material analysis: loss of amino acids during liquid-phase acid hydrolysis

NASA Astrophysics Data System (ADS)

Buch, Arnaud; Brault, Amaury; Szopa, Cyril; Freissinet, Caroline

2015-04-01

Searching for building blocks of life in extraterrestrial material is a way to learn more about how life could have appeared on Earth. With this aim, liquid-phase acid hydrolysis has been used, since at least 1970 , in order to extract amino acids and other organic molecules from extraterrestrial materials (e.g. meteorites, lunar fines) or Earth analogues (e.g. Atacama desert soil). This procedure involves drastic conditions such as heating samples in 6N HCl for 24 h, either under inert atmosphere/vacuum, or air. Analysis of the hydrolyzed part of the sample should give its total (free plus bound) amino acid content. The present work deals with the influence of the 6N HCl hydrolysis on amino acid degradation. Our experiments have been performed on a standard solution of 17 amino acids. After liquid-phase acid hydrolysis (6N HCl) under argon atmosphere (24 h at 100°C), the liquid phase was evaporated and the dry residue was derivatized with N-Methyl-N-(t-butyldimethylsilyl)trifluoroacetamide (MTBSTFA) and dimethylformamide (DMF), followed by gas chromatography-mass spectrometry analysis. After comparison with derivatized amino acids from the standard solution, a significant reduction of the chromatographic peak areas was observed for most of the amino acids after liquid-phase acid hydrolysis. Furthermore, the same loss pattern was observed when the amino acids were exposed to cold 6N HCl for a short amount of time. The least affected amino acid, i.e. glycine, was found to be 73,93% percent less abundant compared to the non-hydrolyzed standard, while the most affected, i.e. histidine, was not found in the chromatograms after hydrolysis. Our experiments thereby indicate that liquid-phase acid hydrolysis, even under inert atmosphere, leads to a partial or total loss of all of the 17 amino acids present in the standard solution, and that a quick cold contact with 6N HCl is sufficient to lead to a loss of amino acids. Therefore, in the literature, the reported increase of the total quantity of amino acids after acid hydrolysis, due to the formation/release of amino acids during the whole water extraction / liquid-phase acid hydrolysis, could have hidden a loss of amino acids. Thus, in extraterrestrial material studies involving liquid-phase acid hydrolysis, the quantities of total amino acids may have been underestimated.

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.

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

NASA Astrophysics Data System (ADS)

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

2013-05-01

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

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

NASA Astrophysics Data System (ADS)

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

2012-12-01

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

(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...

Investigation of flow dynamics of liquid phase in a pilot-scale trickle bed reactor using radiotracer technique.

PubMed

Pant, H J; Sharma, V K

2016-10-01

A radiotracer investigation was carried out to measure residence time distribution (RTD) of liquid phase in a trickle bed reactor (TBR). The main objectives of the investigation were to investigate radial and axial mixing of the liquid phase, and evaluate performance of the liquid distributor/redistributor at different operating conditions. Mean residence times (MRTs), holdups (H) and fraction of flow flowing along different quadrants were estimated. The analysis of the measured RTD curves indicated radial non-uniform distribution of liquid phase across the beds. The overall RTD of the liquid phase, measured at the exit of the reactor was simulated using a multi-parameter axial dispersion with exchange model (ADEM), and model parameters were obtained. The results of model simulations indicated that the TBR behaved as a plug flow reactor at most of the operating conditions used in the investigation. The results of the investigation helped to improve the existing design as well as to design a full-scale industrial TBR for petroleum refining applications. Copyright © 2016 Elsevier Ltd. All rights reserved.

Advanced control of liquid water region in diffusion media of polymer electrolyte fuel cells through a dimensionless number

NASA Astrophysics Data System (ADS)

Wang, Yun; Chen, Ken S.

2016-05-01

In the present work, a three-dimension (3-D) model of polymer electrolyte fuel cells (PEFCs) is employed to investigate the complex, non-isothermal, two-phase flow in the gas diffusion layer (GDL). Phase change in gas flow channels is explained, and a simplified approach accounting for phase change is incorporated into the fuel cell model. It is found that the liquid water contours in the GDL are similar along flow channels when the channels are subject to two-phase flow. Analysis is performed on a dimensionless parameter Da0 introduced in our previous paper [Y. Wang and K. S. Chen, Chemical Engineering Science 66 (2011) 3557-3567] and the parameter is further evaluated in a realistic fuel cell. We found that the GDL's liquid water (or liquid-free) region is determined by the Da0 number which lumps several parameters, including the thermal conductivity and operating temperature. By adjusting these factors, a liquid-free GDL zone can be created even though the channel stream is two-phase flow. Such a liquid-free zone is adjacent to the two-phase region, benefiting local water management, namely avoiding both severe flooding and dryness.

Advanced control of liquid water region in diffusion media of polymer electrolyte fuel cells through a dimensionless number

DOE PAGES

Wang, Yun; Chen, Ken S.

2016-03-21

In the present study, a three-dimension (3-D) model of polymer electrolyte fuel cells (PEFCs) is employed to investigate the complex, non-isothermal, two-phase flow in the gas diffusion layer (GDL). Phase change in gas flow channels is explained, and a simplified approach accounting for phase change is incorporated into the fuel cell model. It is found that the liquid water contours in the GDL are similar along flow channels when the channels are subject to two-phase flow. Here, analysis is performed on a dimensionless parameter Da 0 introduced in our previous paper and the parameter is further evaluated in a realisticmore » fuel cell. We found that the GDL's liquid water (or liquid-free) region is determined by the Da 0 number which lumps several parameters, including the thermal conductivity and operating temperature. By adjusting these factors, a liquid-free GDL zone can be created even though the channel stream is two-phase flow. Such a liquid-free zone is adjacent to the two-phase region, benefiting local water management, namely avoiding both severe flooding and dryness.« less

Automated dynamic liquid-liquid-liquid microextraction followed by high-performance liquid chromatography-ultraviolet detection for the determination of phenoxy acid herbicides in environmental waters.

PubMed

Wu, Jingming; Ee, Kim Huey; Lee, Hian Kee

2005-08-05

Automated dynamic liquid-liquid-liquid microextraction (D-LLLME) controlled by a programmable syringe pump and combined with HPLC-UV was investigated for the extraction and determination of 5 phenoxy acid herbicides in aqueous samples. In the extraction procedure, the acceptor phase was repeatedly withdrawn into and discharged from the hollow fiber by the syringe pump. The repetitive movement of acceptor phase into and out of the hollow fiber channel facilitated the transfer of analytes into donor phase, from the organic phase held in the pore of the fiber. Parameters such as the organic solvent, concentrations of the donor and acceptor phases, plunger movement pattern, speed of agitation and ionic strength of donor phase were evaluated. Good linearity of analytes was achieved in the range of 0.5-500 ng/ml with coefficients of determination, r2 > 0.9994. Good repeatabilities of extraction performance were obtained with relative standard deviations lower than 7.5%. The method provided up-to 490-fold enrichment within 13 min. In addition, the limits of detection (LODs) ranged from 0.1 to 0.4 ng/mL (S/N = 3). D-LLLME was successfully applied for the analysis of phenoxy acid herbicides from real environmental water samples.

Phase relations in the system NaCl-KCl-H2O: V. Thermodynamic-PTX analysis of solid-liquid equilibria at high temperatures and pressures

USGS Publications Warehouse

Sterner, S.M.; Chou, I.-Ming; Downs, R.T.; Pitzer, Kenneth S.

1992-01-01

The Gibbs energies of mixing for NaCl-KCl binary solids and liquids and solid-saturated NaCl-KCl-H2O ternary liquids were modeled using asymmetric Margules treatments. The coefficients of the expressions were calibrated using an extensive array of binary solvus and solidus data, and both binary and ternary liquidus data. Over the PTX range considered, the system exhibits complete liquid miscibility among all three components and extensive solid solution along the anhydrous binary. Solid-liquid and solid-solid phase equilibria were calculated by using the resulting equations and invoking the equality of chemical potentials of NaCl and KCl between appropriate phases at equilibrium. The equations reproduce the ternary liquidus and predict activity coefficients for NaCl and KCl components in the aqueous liquid under solid-saturation conditions between 673 and 1200 K from vapor saturation up to 5 kbar. In the NaCl-KCl anhydrous binary system, the equations describe phase equilibria and predict activity coefficients of the salt components for all stable compositions of solid and liquid phases between room temperature and 1200 K and from 1 bar to 5 kbar. ?? 1992.

Green aspects, developments and perspectives of liquid phase microextraction techniques.

PubMed

Spietelun, Agata; Marcinkowski, Łukasz; de la Guardia, Miguel; Namieśnik, Jacek

2014-02-01

Determination of analytes at trace levels in complex samples (e.g. biological or contaminated water or soils) are often required for the environmental assessment and monitoring as well as for scientific research in the field of environmental pollution. A limited number of analytical techniques are sensitive enough for the direct determination of trace components in samples and, because of that, a preliminary step of the analyte isolation/enrichment prior to analysis is required in many cases. In this work the newest trends and innovations in liquid phase microextraction, like: single-drop microextraction (SDME), hollow fiber liquid-phase microextraction (HF-LPME), and dispersive liquid-liquid microextraction (DLLME) have been discussed, including their critical evaluation and possible application in analytical practice. The described modifications of extraction techniques deal with system miniaturization and/or automation, the use of ultrasound and physical agitation, and electrochemical methods. Particular attention was given to pro-ecological aspects therefore the possible use of novel, non-toxic extracting agents, inter alia, ionic liquids, coacervates, surfactant solutions and reverse micelles in the liquid phase microextraction techniques has been evaluated in depth. Also, new methodological solutions and the related instruments and devices for the efficient liquid phase micoextraction of analytes, which have found application at the stage of procedure prior to chromatographic determination, are presented. © 2013 Published by Elsevier B.V.

Contrasting recovery patterns of 2, 4-dinitrophenylhydrazones (DNPH) derivative of carbonyls between liquid and gas phase standards using HPLC-based analysis

NASA Astrophysics Data System (ADS)

Saha, Subbroto Kumar; Jo, Sang-Hee; Song, Hee-Nam; Brown, Richard J. C.; Kim, Ki-Hyun

2012-12-01

This study evaluates the relative recovery (RR) of five different carbonyls (CCs) (i.e., acetaldehyde, propionaldehyde, butyraldehyde, isovaleraldehyde, and valeraldehyde) following their reaction as 2, 4-dinitrophenylhydrazine (DNPH) derivatives when using gas phase and liquid phase standards. To this end, relative efficiency of CC-DNPH derivatization is compared between two liquid-phase standards (commercially available vs. lab made mixture) and between liquid and gas-phase standard. If the results are compared in terms of response factors (RF) derived for five carbonyls from all different standard phases, the recovery of gaseous CC standard was distinguished from that of liquid counterparts. The RR of the heavier carbonyls (propionaldehyde, butyraldehyde, isovaleraldehyde, and valeraldehyde) was approximately 60% low relative to their liquid counterparts; however, it was not the case for the lighter carbonyls (acetaldehyde) with the RR of ˜92%. This study thus suggests that the quantification of heavy carbonyls in ambient air, unless made by standards of the same matrix (i.e., gas phase) or compensated by the proper correction factor, may be subject to a large bias due to difference in derivatization reaction efficiency between matrix types. Hence, consideration of the matrix effect at the calibration stage is of particular importance to measure CC quantitatively.

Miscibility at the immiscible liquid/liquid interface: A molecular dynamics study of thermodynamics and mechanism

NASA Astrophysics Data System (ADS)

Karnes, John J.; Benjamin, Ilan

2018-01-01

Molecular dynamics simulations are used to study the dissolution of water into an adjacent, immiscible organic liquid phase. Equilibrium thermodynamic and structural properties are calculated during the transfer of water molecule(s) across the interface using umbrella sampling. The net free energy of transfer agrees reasonably well with experimental solubility values. We find that water molecules "prefer" to transfer into the adjacent phase one-at-a-time, without co-transfer of the hydration shell, as in the case of evaporation. To study the dynamics and mechanism of transfer of water to liquid nitrobenzene, we collected over 400 independent dissolution events. Analysis of these trajectories suggests that the transfer of water is facilitated by interfacial protrusions of the water phase into the organic phase, where one water molecule at the tip of the protrusion enters the organic phase by the breakup of a single hydrogen bond.

Micellar-shape anisometry near isotropic-liquid-crystal phase transitions

NASA Astrophysics Data System (ADS)

Itri, R.; Amaral, L. Q.

1993-04-01

Micellar phases of the sodium dodecyl (lauryl) sulfate (SLS)-water-decanol system have been studied by x-ray scattering in the isotropic (I) phase, with emphasis on the I-->hexagonal (Hα) and I-->nematic-cylindrical (Nc) lyotropic liquid-crystal phase transitions. Analysis of the scattering curves is made through modeling of the product P(q)S(q), where P(q) is the micellar form factor and S(q) is the intermicellar interference function, calculated from screened Coulombic repulsion in a mean spherical approximation. Results show that micelles grow more by decanol addition near the I-->Nc transition (anisometry ν~=3) than by increased amphiphile concentration in the binary system near the I-->Hα phase transition (ν~=2.4). These results compare well with recent theories for isotropic-liquid-crystal phase transitions.

Three-phase hollow-fiber liquid-phase microextraction combined with HPLC-UV for the determination of isothiazolinone biocides in adhesives used for food packaging materials.

PubMed

Rosero-Moreano, Milton; Canellas, Elena; Nerín, Cristina

2014-02-01

The present study deals with the development of a liquid microextraction procedure for enhancing the sensitivity of the determination of 2-methyl-4-isothiazolin-3-one and 5-chloro-2-methyl-4-isothiazolin-3-one in adhesives. The procedure involves a three-phase hollow-fiber liquid-phase microextraction using a semipermeable polypropylene membrane, which contained 1-octanol as the organic phase in the pores of the membrane. The donor and acceptor phases are aqueous acidic and alkaline media, respectively, and the final liquid phase (acceptor) is analyzed by HPLC coupled with diode array detection. The most appropriate conditions were extraction time 20 min, stirring speed 1400 rpm, extraction temperature 50°C. The quantification limits of the method were 0.123 and 0.490 μg/g for 2-methyl-4-isothiazolin-3-one and 5-chloro-2-methyl-4-isothiazolin-3-one, respectively. Three different adhesive samples were successfully analyzed. The procedure was compared to direct analysis using ultra high pressure liquid chromatography coupled with TOF-MS, where the identification of the compounds and the quantification values were confirmed. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Nonlinear dynamics of confined thin liquid-vapor bilayer systems with phase change

NASA Astrophysics Data System (ADS)

Kanatani, Kentaro; Oron, Alexander

2011-03-01

We numerically investigate the nonlinear evolution of the interface of a thin liquid-vapor bilayer system confined by rigid horizontal walls from both below and above. The lateral variation of the vapor pressure arising from phase change is taken into account in the present analysis. When the liquid (vapor) is heated (cooled) and gravity acts toward the liquid, the deflection of the interface monotonically grows, leading to a rupture of the vapor layer, whereas nonruptured stationary states are found when the liquid (vapor) is cooled (heated) and gravity acts toward the vapor. In the latter case, vapor-flow-driven convective cells are found in the liquid phase in the stationary state. The average vapor pressure and interface temperature deviate from their equilibrium values once the interface departs from the flat equilibrium state. Thermocapillarity does not have a significant effect near the thermodynamic equilibrium, but becomes important if the system significantly deviates from it.

Melting and Vaporization of the 1223 Phase in the System (Tl-Pb-Ba-Sr-Ca-Cu-O)

PubMed Central

Cook, L. P.; Wong-Ng, W.; Paranthaman, P.

1996-01-01

The melting and vaporization of the 1223 [(Tl,Pb):(Ba,Sr):Ca:Cu] oxide phase in the system (Tl-Pb-Ba-Sr-Ca-Cu-O) have been investigated using a combination of dynamic methods (differential thermal analysis, thermogravimetry, effusion) and post-quenching characterization techniques (powder x-ray diffraction, scanning electron microscopy, energy dispersive x-ray spectrometry). Vaporization rates, thermal events, and melt compositions were followed as a function of thallia loss from a 1223 stoichiometry. Melting and vaporization equilibria of the 1223 phase are complex, with as many as seven phases participating simultaneously. At a total pressure of 0.1 MPa the 1223 phase was found to melt completely at (980 ± 5) °C in oxygen, at a thallia partial pressure (pTl2O) of (4.6 ± 0.5) kPa, where the quoted uncertainties are standard uncertainties, i.e., 1 estimated standard deviation. The melting reaction involves five other solids and a liquid, nominally as follows: 1223→1212+(Ca,Sr)2CuO3+(Sr,Ca)CuO2+BaPbO3+(Ca,Sr)O+Liquid Stoichiometries of the participating phases have been determined from microchemical analysis, and substantial elemental substitution on the 1212 and 1223 crystallographic sites is indicated. The 1223 phase occurs in equilibrium with liquids from its melting point down to at least 935 °C. The composition of the lowest melting liquid detected for the bulk compositions of this study has been measured using microchemical analysis. Applications to the processing of superconducting wires and tapes are discussed. PMID:27805086

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.

Prediction of gas-liquid two-phase flow regime in microgravity

NASA Technical Reports Server (NTRS)

Lee, Jinho; Platt, Jonathan A.

1993-01-01

An attempt is made to predict gas-liquid two-phase flow regime in a pipe in a microgravity environment through scaling analysis based on dominant physical mechanisms. Simple inlet geometry is adopted in the analysis to see the effect of inlet configuration on flow regime transitions. Comparison of the prediction with the existing experimental data shows good agreement, though more work is required to better define some physical parameters. The analysis clarifies much of the physics involved in this problem and can be applied to other configurations.

Preparation, characterization and application of a reversed phase liquid chromatography/hydrophilic interaction chromatography mixed-mode C18-DTT stationary phase.

PubMed

Wang, Qing; Long, Yao; Yao, Lin; Xu, Li; Shi, Zhi-Guo; Xu, Lanying

2016-01-01

A mixed-mode chromatographic stationary phase, C18-DTT (dithiothreitol) silica (SiO2) was prepared through "thiol-ene" click chemistry. The obtained material was characterized by fourier transform infrared spectroscope, nitrogen adsorption analysis and contact angle analysis. Chromatographic performance of the C18-DTT was systemically evaluated by studying the effect of acetonitrile content, pH, buffer concentration of the mobile phase and column temperature. It was demonstrated that the novel stationary phase possessed reversed phase liquid chromatography (RPLC)/hydrophilic interaction liquid chromatography (HILIC) mixed-mode property. The stop-flow test revealed that C18-DTT exhibited excellent compatibility with 100% aqueous mobile phase. Additionally, the stability and column-to-column reproducibility of the C18-DTT material were satisfactory, with relative standard deviations of retention factor of the tested analytes (verapamil, fenbufen, guanine, tetrandrine and nicotinic acid) in the range of 1.82-3.72% and 0.85-1.93%, respectively. Finally, the application of C18-DTT column was demonstrated in the separation of non-steroidal anti-inflammatory drugs, aromatic carboxylic acids, alkaloids, nucleo-analytes and polycyclic aromatic hydrocarbons. It had great resolving power in the analysis of various compounds in HILIC and RPLC chromatographic conditions and was a promising RPLC/HILIC mixed-mode stationary phase. Copyright © 2015 Elsevier B.V. All rights reserved.

On the transition between two-phase and single-phase interface dynamics in multicomponent fluids at supercritical pressures

NASA Astrophysics Data System (ADS)

Dahms, Rainer N.; Oefelein, Joseph C.

2013-09-01

A theory that explains the operating pressures where liquid injection processes transition from exhibiting classical two-phase spray atomization phenomena to single-phase diffusion-dominated mixing is presented. Imaging from a variety of experiments have long shown that under certain conditions, typically when the pressure of the working fluid exceeds the thermodynamic critical pressure of the liquid phase, the presence of discrete two-phase flow processes become diminished. Instead, the classical gas-liquid interface is replaced by diffusion-dominated mixing. When and how this transition occurs, however, is not well understood. Modern theory still lacks a physically based model to quantify this transition and the precise mechanisms that lead to it. In this paper, we derive a new model that explains how the transition occurs in multicomponent fluids and present a detailed analysis to quantify it. The model applies a detailed property evaluation scheme based on a modified 32-term Benedict-Webb-Rubin equation of state that accounts for the relevant real-fluid thermodynamic and transport properties of the multicomponent system. This framework is combined with Linear Gradient Theory, which describes the detailed molecular structure of the vapor-liquid interface region. Our analysis reveals that the two-phase interface breaks down not necessarily due to vanishing surface tension forces, but due to thickened interfaces at high subcritical temperatures coupled with an inherent reduction of the mean free molecular path. At a certain point, the combination of reduced surface tension, the thicker interface, and reduced mean free molecular path enter the continuum length scale regime. When this occurs, inter-molecular forces approach that of the multicomponent continuum where transport processes dominate across the interfacial region. This leads to a continuous phase transition from compressed liquid to supercritical mixture states. Based on this theory, a regime diagram for liquid injection is developed that quantifies the conditions under which classical sprays transition to dense-fluid jets. It is shown that the chamber pressure required to support diffusion-dominated mixing dynamics depends on the composition and temperature of the injected liquid and ambient gas. To illustrate the method and analysis, we use conditions typical of diesel engine injection. We also present a companion set of high-speed images to provide experimental validation of the presented theory. The basic theory is quite general and applies to a wide range of modern propulsion and power systems such as liquid rockets, gas turbines, and reciprocating engines. Interestingly, the regime diagram associated with diesel engine injection suggests that classical spray phenomena at typical injection conditions do not occur.

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.

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.

Simultaneous determination of several phytohormones in natural coconut juice by hollow fiber-based liquid-liquid-liquid microextraction-high performance liquid chromatography.

PubMed

Wu, Yunli; Hu, Bin

2009-11-06

A simple, selective, sensitive and inexpensive method of hollow fiber-based liquid-liquid-liquid microextraction (HF-LLLME) combined with high performance liquid chromatography (HPLC)-ultraviolet (UV) detection was developed for the determination of four acidic phytohormones (salicylic acid (SA), indole-3-acetic acid (IAA), (+/-) abscisic acid (ABA) and (+/-) jasmonic acid (JA)) in natural coconut juice. To the best of our knowledge, this is the first report on the use of liquid phase microextraction (LPME) as a sample pretreatment technique for the simultaneous analysis of several phytohormones. Using phenetole to fill the pores of hollow fiber as the organic phase, 0.1molL(-1) NaOH solution in the lumen of hollow fiber as the acceptor phase and 1molL(-1) HCl as the donor phase, a simultaneous preconcentration of four target phytohormones was realized. The acceptor phase was finally withdrawn into the microsyringe and directly injected into HPLC for the separation and quantification of the target phytohormones. The factors affecting the extraction efficiency of four phytohormones by HF-LLLME were optimized with orthogonal design experiment, and the data was analyzed by Statistical Product and Service Solutions (SPSS) software. Under the optimized conditions, the enrichment factors for SA, IAA, ABA and JA were 243, 215, 52 and 48, with the detection limits (S/N=3) of 4.6, 1.3, 0.9ngmL(-1) and 8.8 microg mL(-1), respectively. The relative standard deviations (RSDs, n=7) were 7.9, 4.9, 6.8% at 50ngmL(-1) level for SA, IAA, ABA and 8.4% at 500 microg mL(-1) for JA, respectively. To evaluate the accuracy of the method, the developed method was applied for the simultaneous analysis of several phytohormones in five natural coconut juice samples, and the recoveries for the spiked samples were in the range of 88.3-119.1%.

Solid-phase microextraction coupled with high performance liquid chromatography: a complementary technique to solid-phase microextraction-gas chromatography for the analysis of pesticide residues in strawberries.

PubMed

Wang, Z; Hennion, B; Urruty, L; Montury, M

2000-11-01

Solid-phase microextraction coupled with high performance liquid chromatography has been studied for the analysis of methiocarb, napropamide, fenoxycarb and bupirimate in strawberries. The strawberries were blended and centrifuged. Then, an aliquot of the resulting extracting solution was subjected to solid-phase microextraction (SPME) on a 60 microns polydimethylsiloxane/divinylbenzene (PDMS/DVB) fibre for 45 min at room temperature. The extracted pesticides on the SPME fibre were desorbed into SPME/high performance liquid chromatography (HPLC) interface for HPLC analysis with diode-array detection (DAD). The method is organic solvent-free for the whole extraction process and is simple and easy to manipulate. The detection limits were shown to be at low microgram kg-1 level and the linear response covered the range from 0.05 to 2 mg kg-1 of pesticides in strawberries with a regression coefficient larger than 0.99. A good repeatability with RSDs between 2.92 and 9.25% was obtained, depending on compounds.

LiOH - H2O2 - H2O trinary system study for the selection of optimal conditions of lithium peroxide synthesis

NASA Astrophysics Data System (ADS)

Nefedov, R. A.; Ferapontov, Yu A.; Kozlova, N. P.

2016-01-01

Using solubility method the decay kinetics of peroxide products contained in liquid phase of LiOH - H2O2 - H2O trinary system with 2 to 6% by wt hydrogen peroxide content in liquid phase in 21 to 33 °C temperature range has been studied. Conducted studies have allowed to determine temperature and concentration limits of solid phase existence of Li2O2·H2O content, distinctness of which has been confirmed using chemical and qualitative X- ray phase analysis. Stabilizing effect of solid phase of Li2O2·H2O content on hydrogen peroxide decay contained in liquid phase of LiOH - H2O2 - H2O trinary system under conditions of experiments conducted has been shown.

Leukotriene B4 catabolism: quantitation of leukotriene B4 and its omega-oxidation products by reversed-phase high-performance liquid chromatography.

PubMed

Shak, S

1987-01-01

LTB4 and its omega-oxidation products may be rapidly, sensitively, and specifically quantitated by the methods of solid-phase extraction and reversed-phase high-performance liquid chromatography (HPLC), which are described in this chapter. Although other techniques, such as radioimmunoassay or gas chromatography-mass spectrometry, may be utilized for quantitative analysis of the lipoxygenase products of arachidonic acid, only the technique of reversed-phase HPLC can quantitate as many as 10 metabolites in a single analysis, without prior derivatization. In this chapter, we also reviewed the chromatographic theory which we utilized in order to optimize reversed-phase HPLC analysis of LTB4 and its omega-oxidation products. With this information and a gradient HPLC system, it is possible for any investigator to develop a powerful assay for the potent inflammatory mediator, LTB4, or for any other lipoxygenase product of arachidonic acid.

Understanding the breakdown of classic two-phase theory and spray atomization at engine-relevant conditions

NASA Astrophysics Data System (ADS)

Dahms, Rainer N.

2016-04-01

A generalized framework for multi-component liquid injections is presented to understand and predict the breakdown of classic two-phase theory and spray atomization at engine-relevant conditions. The analysis focuses on the thermodynamic structure and the immiscibility state of representative gas-liquid interfaces. The most modern form of Helmholtz energy mixture state equation is utilized which exhibits a unique and physically consistent behavior over the entire two-phase regime of fluid densities. It is combined with generalized models for non-linear gradient theory and for liquid injections to quantify multi-component two-phase interface structures in global thermal equilibrium. Then, the Helmholtz free energy is minimized which determines the interfacial species distribution as a consequence. This minimal free energy state is demonstrated to validate the underlying assumptions of classic two-phase theory and spray atomization. However, under certain engine-relevant conditions for which corroborating experimental data are presented, this requirement for interfacial thermal equilibrium becomes unsustainable. A rigorously derived probability density function quantifies the ability of the interface to develop internal spatial temperature gradients in the presence of significant temperature differences between injected liquid and ambient gas. Then, the interface can no longer be viewed as an isolated system at minimal free energy. Instead, the interfacial dynamics become intimately connected to those of the separated homogeneous phases. Hence, the interface transitions toward a state in local equilibrium whereupon it becomes a dense-fluid mixing layer. A new conceptual view of a transitional liquid injection process emerges from a transition time scale analysis. Close to the nozzle exit, the two-phase interface still remains largely intact and more classic two-phase processes prevail as a consequence. Further downstream, however, the transition to dense-fluid mixing generally occurs before the liquid length is reached. The significance of the presented modeling expressions is established by a direct comparison to a reduced model, which utilizes widely applied approximations but fundamentally fails to capture the physical complexity discussed in this paper.

Thermodynamic Modeling of Ag-Ni System Combining Experiments and Molecular Dynamic Simulation

NASA Astrophysics Data System (ADS)

Rajkumar, V. B.; Chen, Sinn-wen

2017-04-01

Ag-Ni is a simple and important system with immiscible liquids and (Ag,Ni) phases. Previously, this system has been thermodynamically modeled utilizing certain thermochemical and phase equilibria information based on conjecture. An attempt is made in this study to determine the missing information which are difficult to measure experimentally. The boundaries of the liquid miscibility gap at high temperatures are determined using a pyrometer. The temperature of the liquid ⇌ (Ag) + (Ni) eutectic reaction is measured using differential thermal analysis. Tie-lines of the Ag-Ni system at 1023 K and 1473 K are measured using a conventional metallurgical method. The enthalpy of mixing of the liquid at 1773 K and the (Ag,Ni) at 973 K is calculated by molecular dynamics simulation using a large-scale atomic/molecular massively parallel simulator. These results along with literature information are used to model the Gibbs energy of the liquid and (Ag,Ni) by a calculation of phase diagrams approach, and the Ag-Ni phase diagram is then calculated.

Characterizing the correlations between local phase fractions of gas-liquid two-phase flow with wire-mesh sensor.

PubMed

Tan, C; Liu, W L; Dong, F

2016-06-28

Understanding of flow patterns and their transitions is significant to uncover the flow mechanics of two-phase flow. The local phase distribution and its fluctuations contain rich information regarding the flow structures. A wire-mesh sensor (WMS) was used to study the local phase fluctuations of horizontal gas-liquid two-phase flow, which was verified through comparing the reconstructed three-dimensional flow structure with photographs taken during the experiments. Each crossing point of the WMS is treated as a node, so the measurement on each node is the phase fraction in this local area. An undirected and unweighted flow pattern network was established based on connections that are formed by cross-correlating the time series of each node under different flow patterns. The structure of the flow pattern network reveals the relationship of the phase fluctuations at each node during flow pattern transition, which is then quantified by introducing the topological index of the complex network. The proposed analysis method using the WMS not only provides three-dimensional visualizations of the gas-liquid two-phase flow, but is also a thorough analysis for the structure of flow patterns and the characteristics of flow pattern transition. This article is part of the themed issue 'Supersensing through industrial process tomography'. © 2016 The Author(s).

Characterizing the correlations between local phase fractions of gas–liquid two-phase flow with wire-mesh sensor

PubMed Central

Liu, W. L.; Dong, F.

2016-01-01

Understanding of flow patterns and their transitions is significant to uncover the flow mechanics of two-phase flow. The local phase distribution and its fluctuations contain rich information regarding the flow structures. A wire-mesh sensor (WMS) was used to study the local phase fluctuations of horizontal gas–liquid two-phase flow, which was verified through comparing the reconstructed three-dimensional flow structure with photographs taken during the experiments. Each crossing point of the WMS is treated as a node, so the measurement on each node is the phase fraction in this local area. An undirected and unweighted flow pattern network was established based on connections that are formed by cross-correlating the time series of each node under different flow patterns. The structure of the flow pattern network reveals the relationship of the phase fluctuations at each node during flow pattern transition, which is then quantified by introducing the topological index of the complex network. The proposed analysis method using the WMS not only provides three-dimensional visualizations of the gas–liquid two-phase flow, but is also a thorough analysis for the structure of flow patterns and the characteristics of flow pattern transition. This article is part of the themed issue ‘Supersensing through industrial process tomography’. PMID:27185959

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

Analysis and comparison of different phase shifters for Stirling pulse tube cryocooler

NASA Astrophysics Data System (ADS)

Lei, Tian; Pfotenhauer, John M.; Zhou, Wenjie

2016-12-01

Investigations of phase shifters and power recovery mechanisms are of sustainable interest for developing Stirling pulse tube cryocoolers (SPTC) with higher power density, more compact design and higher efficiency. This paper investigates the phase shifting capacity and the applications of four different phase shifters, including conventional inertance tube, gas-liquid and spring-oscillator phase shifters, as well as a power recovery displacer. Distributed models based on the electro-acoustic analogy are developed to estimate the phase shifting capacity and the acoustic power dissipation of the three phase shifters without power recovery. The results show that both gas-liquid and spring-oscillator phase shifters have the distinctive capacity of phase shifting with a significant reduction in the inertial component length. Furthermore, full distributed models of SPTCs connected with different phase shifters are developed. The cooling performance of SPTCs using all four phase shifters are presented and typical phase relations are analyzed. The comparison reveals that the power recovery displacer with a more complicated configuration provides the highest efficiency. The gas-liquid and spring-oscillator phase shifters show equivalent efficiency compared with the inertance tube phase shifter. Approximately 10-20% of the acoustic power is dissipated by the phase shifters without power recovery, while 15-20% of the acoustic power can be recovered by the power recovery displacer, leading to a maximum coefficient of performance (COP) above 0.14 at 80 K. A merit analysis is also done by presenting the pros and cons of different phase shifters.

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.

Current trends in sample preparation for cosmetic analysis.

PubMed

Zhong, Zhixiong; Li, Gongke

2017-01-01

The widespread applications of cosmetics in modern life make their analysis particularly important from a safety point of view. There is a wide variety of restricted ingredients and prohibited substances that primarily influence the safety of cosmetics. Sample preparation for cosmetic analysis is a crucial step as the complex matrices may seriously interfere with the determination of target analytes. In this review, some new developments (2010-2016) in sample preparation techniques for cosmetic analysis, including liquid-phase microextraction, solid-phase microextraction, matrix solid-phase dispersion, pressurized liquid extraction, cloud point extraction, ultrasound-assisted extraction, and microwave digestion, are presented. Furthermore, the research and progress in sample preparation techniques and their applications in the separation and purification of allowed ingredients and prohibited substances are reviewed. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Biofilm thickness measurement using an ultrasound method in a liquid phase.

PubMed

Maurício, R; Dias, C J; Jubilado, N; Santana, F

2013-10-01

In this report, the development of an online, noninvasive, measurement method of the biofilm thickness in a liquid phase is presented. The method is based in the analysis of the ultrasound wave pulse-echo behavior in a liquid phase reproducing the real reactor conditions. It does not imply the removal of the biomass from the support or any kind of intervention in the support (pipes) to detect and perform the measurements (non-invasiveness). The developed method allows for its sensor to be easily and quickly mounted and unmounted in any location along a pipe or reactor wall. Finally, this method is an important innovation because it allows the thickness measurement of a biofilm, in liquid phase conditions that can be used in monitoring programs, to help in scheduling cleaning actions to remove the unwanted biofilm, in several application areas, namely in potable water supply pipes.

The Putative Liquid-Liquid Transition is a Liquid-Solid Transition in Atomistic Models of Water

NASA Astrophysics Data System (ADS)

Chandler, David; Limmer, David

2013-03-01

Our detailed and controlled studies of free energy surfaces for models of water find no evidence for reversible polyamorphism, and a general theoretical analysis of the phase behavior of cold water in nano pores shows that measured behaviors of these systems reflect surface modulation and dynamics of ice, not a liquid-liquid critical point. A few workers reach different conclusions, reporting evidence of a liquid-liquid critical point in computer simulations of supercooled water. In some cases, it appears that these contrary results are based upon simulation algorithms that are inconsistent with principles of statistical mechanics, such as using barostats that do not reproduce the correct distribution of volume fluctuations. In other cases, the results appear to be associated with difficulty equilibrating the supercooled material and mistaking metastability for coarsening of the ordered ice phase. In this case, sufficient information is available for us to reproduce the contrary results and to establish that they are artifacts of finite time sampling. This finding leads us to the conclusion that two distinct, reversible liquid phases do not exist in models of supercooled water.

High-pressure liquid-monopropellant strand combustion.

NASA Technical Reports Server (NTRS)

Faeth, G. M.

1972-01-01

Examination of the influence of dissolved gases on the state of the liquid surface during high-pressure liquid-monopropellant combustion through the use of a strand burning experiment. Liquid surface temperatures were measured, using fine-wire thermocouples, during the strand combustion of ethyl nitrate, normal propyl nitrate, and propylene glycol dinitrate at pressures up to 81 atm. These measurements were compared with the predictions of a variable-property gas-phase analysis assuming an infinite activation energy for the decomposition reaction. The state of the liquid surface was estimated using a conventional low-pressure phase equilibrium model, as well as a high-pressure version that considered the presence of dissolved combustion-product gases in the liquid phase. The high-pressure model was found to give a superior prediction of measured liquid surface temperatures. Computed total pressures required for the surface to reach its critical mixing point during strand combustion were found to be in the range from 2.15 to 4.62 times the critical pressure of the pure propellant. Computed dissolved gas concentrations at the liquid surface were in the range from 35 to 50% near the critical combustion condition.

Phase holdups in three-phase fluidized beds in the presence of disc promoter

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

Murty, M.S.N.; Ramesh, K.V.; Venkateswarlu, P.

2011-02-15

Three-phase fluidized beds are found to have wide applications in process industries. The present investigation essentially comprises of the studies on gas holdup, liquid holdup and bed porosity in three-phase fluidized beds with coaxially placed disc promoter. Holdup data were obtained from bed expansion and pressure drop measurements. Analysis of the data was done to elucidate the effects of dynamic and geometric parameters on gas holdup, liquid holdup and bed porosity. Data were correlated and useful equations were obtained from empirical modeling. (author)

Modelling of Hydrophilic Interaction Liquid Chromatography Stationary Phases Using Chemometric Approaches

PubMed Central

Ortiz-Villanueva, Elena; Tauler, Romà

2017-01-01

Metabolomics is a powerful and widely used approach that aims to screen endogenous small molecules (metabolites) of different families present in biological samples. The large variety of compounds to be determined and their wide diversity of physical and chemical properties have promoted the development of different types of hydrophilic interaction liquid chromatography (HILIC) stationary phases. However, the selection of the most suitable HILIC stationary phase is not straightforward. In this work, four different HILIC stationary phases have been compared to evaluate their potential application for the analysis of a complex mixture of metabolites, a situation similar to that found in non-targeted metabolomics studies. The obtained chromatographic data were analyzed by different chemometric methods to explore the behavior of the considered stationary phases. ANOVA-simultaneous component analysis (ASCA), principal component analysis (PCA) and partial least squares regression (PLS) were used to explore the experimental factors affecting the stationary phase performance, the main similarities and differences among chromatographic conditions used (stationary phase and pH) and the molecular descriptors most useful to understand the behavior of each stationary phase. PMID:29064436

Transient-pressure analysis in geothermal steam reservoirs with an immobile vaporizing liquid phase

USGS Publications Warehouse

Moench, A.F.; Atkinson, P.G.

1978-01-01

A finite-difference model for the radial horizontal flow of steam through a porous medium is used to evaluate transient-pressure behavior in the presence of an immobile vaporizing or condensing liquid phase. Graphs of pressure drawdown and buildup in terms of dimensionless pressure and time are obtained for a well discharging steam at a constant mass flow rate for a specified time. The assumptions are made that the steam is in local thermal equilibrium with the reservoir rocks, that temperature changes are due only to phase change, and that effects of vapor-pressure lowering are negligible. Computations show that when a vaporizing liquid phase is present the pressure drawdown exhibits behavior similar to that observed in noncondensable gas reservoirs, but delayed in time. A theoretical analysis allows for the computation of this delay and demonstrates that it is independent of flow geometry. The response that occurs upon pressure buildup is markedly different from that in a noncondensable gas system. This result may provide a diagnostic tool for establishing the existence of phase-change phenomena within a reservoir. ?? 1979.

Dicyanamide Salts that Adopt Smectic, Columnar, or Bicontinuous Cubic Liquid-Crystalline Mesophases.

PubMed

Park, Geonhui; Goossens, Karel; Shin, Tae Joo; Bielawski, Christopher W

2018-04-25

Although dicyanamide (i.e., [N(CN) 2 ] - ) has been commonly used to obtain low-viscosity, halogen-free, room-temperature ionic liquids, liquid-crystalline salts containing such anions have remained virtually unexplored. Here we report a series of amphiphilic dicyanamide salts that, depending on their structures and compositions, adopt smectic, columnar, or bicontinuous cubic thermotropic liquid-crystalline mesophases, even at room temperature in some cases. Their thermal properties were explored by polarized light optical microscopy, differential scanning calorimetry, thermogravimetric analysis (including evolved gas analysis), and variable-temperature synchrotron X-ray diffraction. Comparison of the thermal phase characteristics of these new liquid-crystalline salts featuring "V-shaped" [N(CN) 2 ] - anions with those of structural analogues containing [SCN] - , [BF 4 ] - , [PF 6 ] - , or [CF 3 SO 3 ] - anions indicated that not only the size of the counterion but also its shape should be considered in the development of mesomorphic salts. Collectively, these discoveries may be expected to facilitate the design of thermotropic ionic liquid crystals that form inverted-type bicontinuous cubic and other sophisticated liquid-crystalline phases. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Parallel mass spectrometry (APCI-MS and ESI-MS) for lipid analysis

USDA-ARS?s Scientific Manuscript database

Coupling the condensed phase of HPLC with the high vacuum necessary for ion analysis in a mass spectrometer requires quickly evaporating large amounts of liquid mobile phase to release analyte molecules into the gas phase, along with ionization of those molecules, so they can be detected by the mass...

Sheath liquid interface for the coupling of normal-phase liquid chromatography with electrospray mass spectrometry and its application to the analysis of neoflavonoids.

PubMed

Charles, Laurence; Laure, Frédéric; Raharivelomanana, Phila; Bianchini, Jean-Pierre

2005-01-01

A novel interface that allows normal-phase liquid chromatography to be coupled with electrospray ionization (ESI) is reported. A make-up solution of 60 mM ammonium acetate in methanol, infused at a 5 microl min(-1) flow-rate at the tip of the electrospray probe, provides a sheath liquid which is poorly miscible with the chromatographic effluent, but promotes efficient ionization of the targeted analytes. Protonated molecules generated in the ESI source were subjected to tandem mass spectrometric experiments in a triple-quadrupole mass spectrometer. The main fragmentation reactions were characterized for each analyte and specific mass spectral transitions were used to acquire chromatographic data in the multiple reaction monitoring detection mode. Results obtained during optimization of the sheath liquid composition and flow-rate suggest that the electrospray process was mainly under the control of the make-up solution, and that it forms an external charged layer around a neutral chromatographic mobile phase core. This sheath liquid interface was implemented for the analysis of some neoflavonoid compounds and its performance was evaluated. Limits of detection were established for calophillolide, inophyllum B, inophyllum P and inophyllum C at 100, 25, 15 and 100 ng ml(-1), respectively.

High Performance Liquid Chromatography of Some Analgesic Compounds: An Instrumental Analysis Experiment.

ERIC Educational Resources Information Center

Haddad, Paul; And Others

1983-01-01

Background information, procedures, and results are provided for an experiment demonstrating techniques of solvent selection, gradient elution, pH control, and ion-pairing in the analysis of an analgesic mixture using reversed-phase liquid chromatography on an octadecylsilane column. Although developed using sophisticated/expensive equipment, less…

Quality evaluation of moluodan concentrated pill using high-performance liquid chromatography fingerprinting coupled with chemometrics.

PubMed

Tao, Lingyan; Zhang, Qing; Wu, Yongjiang; Liu, Xuesong

2016-12-01

In this study, a fast and effective high-performance liquid chromatography method was developed to obtain a fingerprint chromatogram and quantitative analysis simultaneously of four indexes including gallic acid, chlorogenic acid, albiflorin and paeoniflorin of the traditional Chinese medicine Moluodan Concentrated Pill. The method was performed by using a Waters X-bridge C 18 reversed phase column on an Agilent 1200S high-performance liquid chromatography system coupled with diode array detection. The mobile phase of the high-performance liquid chromatography method was composed of 20 mmol/L phosphate solution and acetonitrile with a 1 mL/min eluent velocity, under a detection temperature of 30°C and a UV detection wavelength of 254 nm. After the methodology validation, 16 batches of Moluodan Concentrated Pill were analyzed by this high-performance liquid chromatography method and both qualitative and quantitative evaluation results were achieved by similarity analysis, principal component analysis and hierarchical cluster analysis. The results of these three chemometrics were in good agreement and all indicated that batch 10 and batch 16 showed significant differences with the other 14 batches. This suggested that the developed high-performance liquid chromatography method could be applied in the quality evaluation of Moluodan Concentrated Pill. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Study of axial mixing, holdup and slip velocity of dispersed phase in a pulsed sieve plate extraction column using radiotracer technique.

PubMed

Ghiyas Ud Din; Imran Rafiq Chughtai; Hameed Inayat, Mansoor; Hussain Khan, Iqbal

2009-01-01

Axial mixing, holdup and slip velocity of dispersed phase which are parameters of fundamental importance in the design and operation of liquid-liquid extraction pulsed sieve plate columns have been investigated. Experiments for residence time distribution (RTD) analysis have been carried out for a range of pulsation frequency and amplitude in a liquid-liquid extraction pulsed sieve plate column with water as dispersed and kerosene as continuous phase using radiotracer technique. The column was operated in emulsion region and (99m)Tc in the form of sodium pertechnetate eluted from a (99)Mo/(99m)Tc generator was used to trace the dispersed phase. Axial dispersed plug flow model with open-open boundary condition and two points measurement method was used to simulate the hydrodynamics of dispersed phase. It has been observed that the axial mixing and holdup of dispersed phase increases with increase in pulsation frequency and amplitude until a maximum value is achieved while slip velocity decreases with increase in pulsation frequency and amplitude until it approaches a minimum value. Short lived and low energy radiotracer (99m)Tc in the form of sodium pertechnetate was found to be a good water tracer to study the hydrodynamics of a liquid-liquid extraction pulsed sieve plate column operating with two immiscible liquids, water and kerosene. Axial dispersed plug flow model with open-open boundary condition was found to be a suitable model to describe the hydrodynamics of dispersed phase in the pulsed sieve plate extraction column.

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.

Unsteady numerical analysis of solid-liquid two-phase flow in stirred tank with double helical ribbon impeller

NASA Astrophysics Data System (ADS)

Bai, He; Chen, Xiangshan; Zhao, Guangyu; Xiao, Chenglei; Li, Chen; Zhong, Cheng; Chen, Yu

2017-08-01

In order to enhance the mixing process of soil contaminated by oil and water, one kind of double helical ribbon (DHR) impeller was developed. In this study, the unsteady simulation analysis of solid-liquid two-phase flow in stirring tank with DHR impeller was conducted by the the computational fluid dynamics and the multi-reference frame (MRF) method. It was found that at 0-3.0 s stage, the rate of liquid was greater than the rate of solid particles, while the power consumption was 5-6 times more than the smooth operation. The rates of the liquid and the solid particles were almost the same, and the required power was 32 KW at t > 3.0 s. The flow of the solid particles in the tank was a typical axial circle flow, and the dispersed sequence of the solid that was accumulated at the bottom of the tank was: the bottom loop region, the annular region near the wall of the groove and finally the area near axial center. The results show that the DHR impeller was suitable for the mixing of liquid-solid two-phase.

Method for Predicting Hypergolic Mixture Flammability Limits

DTIC Science & Technology

2017-02-01

liquid phase, in the gas phase, at the liquid / liquid interface and at the gas / liquid interface during hypergolic ignition and the interactions...of what happens in the liquid phase, in the gas phase, at the liquid / liquid interface and at the gas / liquid interface during hypergolic ignition...and the interactions of all these phases. The ignition happens in the gas -phase but products formed here and there (in the liquid phase or at

Formation of iron complexs from trifluoroacetic acid based liquid chromatography mobile phases as interference ions in liquid chromatography/electrospray ionization mass spectrometric analysis

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

Shukla, Anil K.; Zhang, Rui; Orton, Daniel J.

Two unexpected singly charged ions at m/z 1103 and 944 have been observed in mass spectra obtained from electrospray ionization-mass spectrometric analysis of liquid chromatography effluents with mobile phases containing trifluoroacetic acid. Accurate mass measurement and tandem mass spectrometry studies revealed that these two ions are not due to any contamination from solvents and chemicals used for mobile and stationary phases or from the laboratory atmospheric environment. Instead these ions are clusters of trifluoroacetic acid formed in association with acetonitrile, water and iron from the stainless steel union used to connect the column with the electrospray tip and to applymore » high voltage; the molecular formulae are Fe+((OH)(H2O)2)9(CF3COOH)5 and Fe+((OH)(H2O)2)6 (CF3COOH)5.« less

Using artificial intelligence to improve identification of nanofluid gas-liquid two-phase flow pattern in mini-channel

NASA Astrophysics Data System (ADS)

Xiao, Jian; Luo, Xiaoping; Feng, Zhenfei; Zhang, Jinxin

2018-01-01

This work combines fuzzy logic and a support vector machine (SVM) with a principal component analysis (PCA) to create an artificial-intelligence system that identifies nanofluid gas-liquid two-phase flow states in a vertical mini-channel. Flow-pattern recognition requires finding the operational details of the process and doing computer simulations and image processing can be used to automate the description of flow patterns in nanofluid gas-liquid two-phase flow. This work uses fuzzy logic and a SVM with PCA to improve the accuracy with which the flow pattern of a nanofluid gas-liquid two-phase flow is identified. To acquire images of nanofluid gas-liquid two-phase flow patterns of flow boiling, a high-speed digital camera was used to record four different types of flow-pattern images, namely annular flow, bubbly flow, churn flow, and slug flow. The textural features extracted by processing the images of nanofluid gas-liquid two-phase flow patterns are used as inputs to various identification schemes such as fuzzy logic, SVM, and SVM with PCA to identify the type of flow pattern. The results indicate that the SVM with reduced characteristics of PCA provides the best identification accuracy and requires less calculation time than the other two schemes. The data reported herein should be very useful for the design and operation of industrial applications.

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.

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.

Definition of two-phase flow behaviors for spacecraft design

NASA Technical Reports Server (NTRS)

Reinarts, Thomas R.; Best, Frederick R.; Miller, Katherine M.; Hill, Wayne S.

1991-01-01

Data for complete models of two-phase flow in microgravity are taken from in-flight experiments and applied to an adiabatic flow-regime analysis to study the feasibility of two-phase systems for spacecraft. The data are taken from five in-flight experiments by Hill et al. (1990) in which a two-phase pump circulates a freon mixture and vapor and liquid flow streams are measured. Adiabatic flow regimes are analyzed based on the experimental superficial velocities of liquid and vapor, and comparisons are made with the results of two-phase flow regimes at 1 g. A motion analyzer records the flow characteristics at a rate of 1000 frames/sec, and stratified flow regimes are reported at 1 g. The flow regimes observed under microgravitational conditions are primarily annular and include slug and bubbly-slug regimes. The present data are of interest to the design and analysis of two-phase thermal-management systems for use in space missions.

Liquid and vapour-phase antifungal activities of selected essential oils against candida albicans: microscopic observations and chemical characterization of cymbopogon citratus

PubMed Central

2010-01-01

Background Use of essential oils for controlling Candida albicans growth has gained significance due to the resistance acquired by pathogens towards a number of widely-used drugs. The aim of this study was to test the antifungal activity of selected essential oils against Candida albicans in liquid and vapour phase and to determine the chemical composition and mechanism of action of most potent essential oil. Methods Minimum Inhibitory concentration (MIC) of different essential oils in liquid phase, assayed through agar plate dilution, broth dilution & 96-well micro plate dilution method and vapour phase activity evaluated through disc volatilization method. Reduction of C. albicans cells with vapour exposure was estimated by kill time assay. Morphological alteration in treated/untreated C. albicans cells was observed by the Scanning electron microscopy (SEM)/Atomic force microscopy (AFM) and chemical analysis of the strongest antifungal agent/essential oil has been done by GC, GC-MS. Results Lemon grass (Cymbopogon citratus) essential oil exhibited the strongest antifungal effect followed by mentha (Mentha piperita) and eucalyptus (Eucalyptus globulus) essential oil. The MIC of lemon grass essential oil in liquid phase (288 mg/l) was significantly higher than that in the vapour phase (32.7 mg/l) and a 4 h exposure was sufficient to cause 100% loss in viability of C. albicans cells. SEM/AFM of C. albicans cells treated with lemon grass essential oil at MIC level in liquid and vapour phase showed prominent shrinkage and partial degradation, respectively, confirming higher efficacy of vapour phase. GC-MS analysis revealed that lemon grass essential oil was dominated by oxygenated monoterpenes (78.2%); α-citral or geranial (36.2%) and β-citral or neral (26.5%), monoterpene hydrocarbons (7.9%) and sesquiterpene hydrocarbons (3.8%). Conclusion Lemon grass essential oil is highly effective in vapour phase against C. albicans, leading to deleterious morphological changes in cellular structures and cell surface alterations. PMID:21067604

Role of Hf on Phase Formation in Ti45Zr(38-x)Hf(x)Ni17 Liquids and Solids

NASA Technical Reports Server (NTRS)

Wessels, V.; Sahu, K. K.; Gangopadhyay, A. K.; Huett, V. T.; Canepari, S.; Goldman, A. I.; Hyers, R. W.; Kramer, M. J.; Rogers, J. R.; Kelton, K. F.;

On The Validity of the Assumed PDF Method for Modeling Binary Mixing/Reaction of Evaporated Vapor in GAS/Liquid-Droplet Turbulent Shear Flow

NASA Technical Reports Server (NTRS)

Miller, R. S.; Bellan, J.

1997-01-01

An Investigation of the statistical description of binary mixing and/or reaction between a carrier gas and an evaporated vapor species in two-phase gas-liquid turbulent flows is perfomed through both theroetical analysis and comparisons with results from direct numerical simulations (DNS) of a two-phase mixing layer.

Reversed-phase high-performance liquid chromatography of sulfur mustard in water

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

Raghuveeran, C.D.; Malhotra, R.C.; Dangi, R.S.

1993-01-01

A reversed-phase high-performance liquid chromatography method for the detection and quantitation of sulfur mustard (HD) in water is described with detection at 200 nm. The detection based on the solubility of HD in water revealed that extremely low quantities of HD (4 to 5 mg/L) only are soluble. Experience shows that water is still the medium of choice for the analysis of HD in water and aqueous effluents in spite of the minor handicap of its half-life of ca. 4 minutes, which only calls for speedy analysis.

Aqueous two-phase based on ionic liquid liquid-liquid microextraction for simultaneous determination of five synthetic food colourants in different food samples by high-performance liquid chromatography.

PubMed

Sha, Ou; Zhu, Xiashi; Feng, Yanli; Ma, Weixing

2015-05-01

A rapid and effective method of aqueous two-phase systems based on ionic liquid microextraction for the simultaneous determination of five synthetic food colourants (tartrazine, sunset yellow, amaranth, ponceau 4R and brilliant blue) in food samples was established. High-performance liquid chromatography coupled with an ultraviolet detector of variable wavelength was used for the determinations. 1-alkyl-3-methylimidazolium bromide was selected as the extraction reagent. The extraction efficiency of the five colourants in the proposed system is influenced by the types of salts, concentrations of salt and [CnMIM]Br, as well as the extracting time. Under the optimal conditions, the extraction efficiencies for these five colourants were above 95%. The phase behaviours of aqueous two-phase system and extraction mechanism were investigated by UV-vis spectroscopy. This method was applied to the analysis of the five colourants in real food samples with the detection limit of 0.051-0.074 ng/mL. Good spiked recoveries from 93.2% to 98.9% were obtained. Copyright © 2014 Elsevier Ltd. All rights reserved.

Wideband digital frequency detector with subtraction-based phase comparator for frequency modulation atomic force microscopy.

PubMed

Mitani, Yuji; Kubo, Mamoru; Muramoto, Ken-ichiro; Fukuma, Takeshi

2009-08-01

We have developed a wideband digital frequency detector for high-speed frequency modulation atomic force microscopy (FM-AFM). We used a subtraction-based phase comparator (PC) in a phase-locked loop circuit instead of a commonly used multiplication-based PC, which has enhanced the detection bandwidth to 100 kHz. The quantitative analysis of the noise performance revealed that the internal noise from the developed detector is small enough to provide the theoretically limited noise performance in FM-AFM experiments in liquid. FM-AFM imaging of mica in liquid was performed with the developed detector, showing its stability and applicability to true atomic-resolution imaging in liquid.

Direct Sampling and Analysis from Solid Phase Extraction Cards using an Automated Liquid Extraction Surface Analysis Nanoelectrospray Mass Spectrometry System

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

Walworth, Matthew J; ElNaggar, Mariam S; Stankovich, Joseph J

Direct liquid extraction based surface sampling, a technique previously demonstrated with continuous flow and autonomous pipette liquid microjunction surface sampling probes, has recently been implemented as the Liquid Extraction Surface Analysis (LESA) mode on the commercially available Advion NanoMate chip-based infusion nanoelectrospray ionization system. In the present paper, the LESA mode was applied to the analysis of 96-well format custom solid phase extraction (SPE) cards, with each well consisting of either a 1 or 2 mm diameter monolithic hydrophobic stationary phase. These substrate wells were conditioned, loaded with either single or multi-component aqueous mixtures, and read out using the LESAmore » mode of a TriVersa NanoMate or a Nanomate 100 coupled to an ABI/Sciex 4000QTRAPTM hybrid triple quadrupole/linear ion trap mass spectrometer and a Thermo LTQ XL linear ion trap mass spectrometer. Extraction conditions, including extraction/nanoESI solvent composition, volume, and dwell times, were optimized in the analysis of targeted compounds. Limit of detection and quantitation as well as analysis reproducibility figures of merit were measured. Calibration data was obtained for propranolol using a deuterated internal standard which demonstrated linearity and reproducibility. A 10x increase in signal and cleanup of micromolar Angiotensin II from a concentrated salt solution was demonstrated. Additionally, a multicomponent herbicide mixture at ppb concentration levels was analyzed using MS3 spectra for compound identification in the presence of isobaric interferences.« less

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

Ionic liquid-anionic surfactant based aqueous two-phase extraction for determination of antibiotics in honey by high-performance liquid chromatography.

PubMed

Yang, Xiao; Zhang, Shaohua; Yu, Wei; Liu, Zhongling; Lei, Lei; Li, Na; Zhang, Hanqi; Yu, Yong

2014-06-01

An ionic liquid-anionic surfactant based aqueous two-phase extraction was developed and applied for the extraction of tetracycline, oxytetracycline and chloramphenicol in honey. The honey sample was mixed with Na2EDTA aqueous solution. The sodium dodecyl sulfate, ionic liquid 1-octyl-3-methylimidazolium bromide and sodium chloride were added in the mixture. After the resulting mixture was ultrasonically shaken and centrifuged, the aqueous two phase system was formed and analytes were extracted into the upper phase. The parameters affecting the extraction efficiency, such as the volume of ionic liquid, the category and amount of salts, sample pH value, extraction time and temperature were investigated. The limits of detection of tetracycline, oxytetracycline and chloramphenicol were 5.8, 8.2 and 4.2 μg kg(-1), respectively. When the present method was applied to the analysis of real honey samples, the recoveries of analytes ranged from 85.5 to 110.9% and relative standard deviations were lower than 6.9%. Copyright © 2014 Elsevier B.V. All rights reserved.

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.

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.

Analysis of antimycin A by reversed-phase liquid chromatography/nuclear magnetic-resonance spectrometry

USGS Publications Warehouse

Ha, Steven T.K.; Wilkins, Charles L.; Abidi, Sharon L.

1989-01-01

A mixture of closely related streptomyces fermentation products, antimycin A, Is separated, and the components are identified by using reversed-phase high-performance liquid chromatography with directly linked 400-MHz proton nuclear magnetic resonance detection. Analyses of mixtures of three amino acids, alanine, glycine, and valine, are used to determine optimal measurement conditions. Sensitivity increases of as much as a factor of 3 are achieved, at the expense of some loss in chromatographic resolution, by use of an 80-μL NMR cell, Instead of a smaller 14-μL cell. Analysis of the antimycin A mixture, using the optimal analytical high performance liquid chromatography/nuclear magnetic resonance conditions, reveals it to consist of at least 10 closely related components.

Instrumental Analysis in Environmental Chemistry - Liquid and Solid Phase Detection Systems

ERIC Educational Resources Information Center

Stedman, Donald H.; Meyers, Philip A.

1974-01-01

This is the second of two reviews dealing with analytical methods applicable to environmental chemistry. Methods are discussed under gas, liquid, or solid depending upon the state of the analyte during detection. (RH)

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.

Understanding the breakdown of classic two-phase theory and spray atomization at engine-relevant conditions

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

Dahms, Rainer N.

A generalized framework for multi-component liquid injections is presented to understand and predict the breakdown of classic two-phase theory and spray atomization at engine-relevant conditions. The analysis focuses on the thermodynamic structure and the immiscibility state of representative gas-liquid interfaces. The most modern form of Helmholtz energy mixture state equation is utilized which exhibits a unique and physically consistent behavior over the entire two-phase regime of fluid densities. It is combined with generalized models for non-linear gradient theory and for liquid injections to quantify multi-component two-phase interface structures in global thermal equilibrium. Then, the Helmholtz free energy is minimized whichmore » determines the interfacial species distribution as a consequence. This minimal free energy state is demonstrated to validate the underlying assumptions of classic two-phase theory and spray atomization. However, under certain engine-relevant conditions for which corroborating experimental data are presented, this requirement for interfacial thermal equilibrium becomes unsustainable. A rigorously derived probability density function quantifies the ability of the interface to develop internal spatial temperature gradients in the presence of significant temperature differences between injected liquid and ambient gas. Then, the interface can no longer be viewed as an isolated system at minimal free energy. Instead, the interfacial dynamics become intimately connected to those of the separated homogeneous phases. Hence, the interface transitions toward a state in local equilibrium whereupon it becomes a dense-fluid mixing layer. A new conceptual view of a transitional liquid injection process emerges from a transition time scale analysis. Close to the nozzle exit, the two-phase interface still remains largely intact and more classic two-phase processes prevail as a consequence. Further downstream, however, the transition to dense-fluid mixing generally occurs before the liquid length is reached. As a result, the significance of the presented modeling expressions is established by a direct comparison to a reduced model, which utilizes widely applied approximations but fundamentally fails to capture the physical complexity discussed in this paper.« less

Understanding the breakdown of classic two-phase theory and spray atomization at engine-relevant conditions

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

Dahms, Rainer N., E-mail: Rndahms@sandia.gov

A generalized framework for multi-component liquid injections is presented to understand and predict the breakdown of classic two-phase theory and spray atomization at engine-relevant conditions. The analysis focuses on the thermodynamic structure and the immiscibility state of representative gas-liquid interfaces. The most modern form of Helmholtz energy mixture state equation is utilized which exhibits a unique and physically consistent behavior over the entire two-phase regime of fluid densities. It is combined with generalized models for non-linear gradient theory and for liquid injections to quantify multi-component two-phase interface structures in global thermal equilibrium. Then, the Helmholtz free energy is minimized whichmore » determines the interfacial species distribution as a consequence. This minimal free energy state is demonstrated to validate the underlying assumptions of classic two-phase theory and spray atomization. However, under certain engine-relevant conditions for which corroborating experimental data are presented, this requirement for interfacial thermal equilibrium becomes unsustainable. A rigorously derived probability density function quantifies the ability of the interface to develop internal spatial temperature gradients in the presence of significant temperature differences between injected liquid and ambient gas. Then, the interface can no longer be viewed as an isolated system at minimal free energy. Instead, the interfacial dynamics become intimately connected to those of the separated homogeneous phases. Hence, the interface transitions toward a state in local equilibrium whereupon it becomes a dense-fluid mixing layer. A new conceptual view of a transitional liquid injection process emerges from a transition time scale analysis. Close to the nozzle exit, the two-phase interface still remains largely intact and more classic two-phase processes prevail as a consequence. Further downstream, however, the transition to dense-fluid mixing generally occurs before the liquid length is reached. The significance of the presented modeling expressions is established by a direct comparison to a reduced model, which utilizes widely applied approximations but fundamentally fails to capture the physical complexity discussed in this paper.« less

Understanding the breakdown of classic two-phase theory and spray atomization at engine-relevant conditions

DOE PAGES

Dahms, Rainer N.

2016-04-26

A generalized framework for multi-component liquid injections is presented to understand and predict the breakdown of classic two-phase theory and spray atomization at engine-relevant conditions. The analysis focuses on the thermodynamic structure and the immiscibility state of representative gas-liquid interfaces. The most modern form of Helmholtz energy mixture state equation is utilized which exhibits a unique and physically consistent behavior over the entire two-phase regime of fluid densities. It is combined with generalized models for non-linear gradient theory and for liquid injections to quantify multi-component two-phase interface structures in global thermal equilibrium. Then, the Helmholtz free energy is minimized whichmore » determines the interfacial species distribution as a consequence. This minimal free energy state is demonstrated to validate the underlying assumptions of classic two-phase theory and spray atomization. However, under certain engine-relevant conditions for which corroborating experimental data are presented, this requirement for interfacial thermal equilibrium becomes unsustainable. A rigorously derived probability density function quantifies the ability of the interface to develop internal spatial temperature gradients in the presence of significant temperature differences between injected liquid and ambient gas. Then, the interface can no longer be viewed as an isolated system at minimal free energy. Instead, the interfacial dynamics become intimately connected to those of the separated homogeneous phases. Hence, the interface transitions toward a state in local equilibrium whereupon it becomes a dense-fluid mixing layer. A new conceptual view of a transitional liquid injection process emerges from a transition time scale analysis. Close to the nozzle exit, the two-phase interface still remains largely intact and more classic two-phase processes prevail as a consequence. Further downstream, however, the transition to dense-fluid mixing generally occurs before the liquid length is reached. As a result, the significance of the presented modeling expressions is established by a direct comparison to a reduced model, which utilizes widely applied approximations but fundamentally fails to capture the physical complexity discussed in this paper.« less

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.

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.

Growth Kinetics of Intracellular RNA/Protein Droplets: Signature of a Liquid-Liquid Phase Transition?

NASA Astrophysics Data System (ADS)

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

2015-03-01

Nonmembrane-bound organelles are functional, dynamic assemblies of RNA and/or protein that can self-assemble and disassemble within the cytoplasm or nucleoplasm. The possibility that underlying intracellular phase transitions may drive and mediate the morphological evolution of some membrane-less organelles has been supported by several recent studies. In this talk, results from a collaborative experimental-theoretical study of the growth and dissolution kinetics of nucleoli and extranucleolar droplets (ENDs) in C. elegans embryos will be presented. We have employed Flory-Huggins solution theory, reaction-diffusion kinetics, and quantitative statistical dynamic scaling analysis to characterize the specific growth mechanisms at work. Our findings indicate that both in vivo and in vitro droplet scaling and growth kinetics are consistent with those resulting from an equilibrium liquid-liquid phase transition mediated by passive nonequilibrium growth mechanisms - simultaneous Brownian coalescence and Ostwald ripening. This supports a view in which cells can employ phase transitions to drive structural organization, while utilizing active processes, such as local transcriptional activity, to fine tune the kinetics of these phase transitions in response to given conditions.

Development of an Alternative Mixed Odor Delivery Device (MODD) for Canine Training

DTIC Science & Technology

2017-05-10

solid phase microextraction (SPME) and analysis by gas chromatography / mass spectrometry (GC/MS). Like the computational modeling, the laboratory...outlet was extracted by solid phase microextraction (SPME) and analyzed by gas chromatography with mass spectrometry (GC/MS). A polydimethylsiloxane...Menning and H. Ostmark, "Detection of liquid and homemade explosives: What do we need to know about their properties?," in Detection of Liquid

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.

Simultaneous analysis of different classes of phytohormones in coconut (Cocos nucifera L.) water using high-performance liquid chromatography and liquid chromatography-tandem mass spectrometry after solid-phase extraction.

PubMed

Ma, Zhen; Ge, Liya; Lee, Anna S Y; Yong, Jean Wan Hong; Tan, Swee Ngin; Ong, Eng Shi

2008-03-10

Coconut (Cocos nucifera L.) water, which contains many uncharacterized phytohormones is extensively used as a growth promoting supplement in plant tissue culture. In this paper, a high-performance liquid chromatography (HPLC) method was developed for the simultaneous determination of various classes phytohormones, including indole-3-acetic acid (IAA), indole-3-butyric acid (IBA), abscisic acid (ABA), gibberellic acid (GA), zeatin (Z), N(6)-benzyladenine (BA), alpha-naphthaleneacetic acid (NAA) and 2,4-dichlorophenoxyacetic acid (2,4-D) in young coconut water (CW). The analysis was carried out using a reverse-phase HPLC gradient elution, with an aqueous mobile phase (containing 0.1% formic acid, pH adjusted to 3.2 with triethylamine (TEA)) modified by methanol, and solute detection made at 265 nm wavelength. The method was validated for specificity, quantification, accuracy and precision. After preconcentration of putative endogenous phytohormones in CW using C(18) solid-phase extraction (SPE) cartridges, the HPLC method was able to screen for putative endogenous phytohormones present in CW. Finally, the identities of the putative phytohormones present in CW were further confirmed using independent liquid chromatography-tandem mass spectrometry (LC-MS/MS) equipped with an electrospray ionization (ESI) interface.

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.

Thermal and Fluid Mechanical Investigation of an Internally Cooled Piston Rod

NASA Astrophysics Data System (ADS)

Klotsche, K.; Thomas, C.; Hesse, U.

2017-08-01

The Internal Cooling of Reciprocating Compressor Parts (ICRC) is a promising technology to reduce the temperature of the thermally stressed piston and piston rod of process gas compressors. The underlying heat transport is based on the flow of a two-phase cooling medium that is contained in the hollow reciprocating assembly. The reciprocating motion forces the phases to mix, enabling an enhanced heat transfer. In order to investigate this heat transfer, experimental results from a vertically reciprocating hollow rod are presented that show the influence of different liquid charges for different working temperatures. In addition, pressure sensors are used for a crank angle dependent analysis of the fluid mechanical processes inside the rod. The results serve to investigate the two-phase flow in terms of the velocity and distribution of the liquid and vapour phase for different liquid fractions.

Microwave-immobilized polybutadiene stationary phase for reversed-phase high-performance liquid chromatography.

PubMed

Lopes, Nilva P; Collins, Kenneth E; Jardim, Isabel C S F

2004-03-19

Polybutadiene (PBD) has been immobilized on high-performance liquid chromatography (HPLC) silica by microwave radiation at various power levels (52-663 W) and actuation times (3-60 min). Columns prepared from these reversed-phase HPLC materials, as well as from similar non-irradiated materials, were tested with standard sample mixtures and characterized by elemental analysis (%C) and infrared spectroscopy. A microwave irradiation of 20 min at 663 W gives a layer of immobilized PBD that presented good performance. Longer irradiation times give thicker immobilized layers having less favorable chromatographic properties.

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.

Lead(ii) soaps: crystal structures, polymorphism, and solid and liquid mesophases.

PubMed

Martínez-Casado, F J; Ramos-Riesco, M; Rodríguez-Cheda, J A; Redondo-Yélamos, M I; Garrido, L; Fernández-Martínez, A; García-Barriocanal, J; da Silva, I; Durán-Olivencia, M; Poulain, A

2017-07-05

The long-chain members of the lead(ii) alkanoate series or soaps, from octanoate to octadecanoate, have been thoroughly characterized by means of XRD, PDF analysis, DSC, FTIR, ssNMR and other techniques, in all their phases and mesophases. The crystal structures at room temperature of all of the members of the series are now solved, showing the existence of two polymorphic forms in the room temperature crystal phase, different to short and long-chain members. Only nonanoate and decanoate present both forms, and this polymorphism is proven to be monotropic. At higher temperature, these compounds present a solid mesophase, defined as rotator, a liquid crystal phase and a liquid phase, all of which have a similar local arrangement. Since some lead(ii) soaps appear as degradation compounds in oil paintings, the solved crystal structures of lead(ii) soaps can now be used as fingerprints for their detection using X-ray diffraction. Pair distribution function analysis on these compounds is very similar in the same phases and mesophases for the different members, showing the same short range order. This observation suggests that this technique could also be used in the detection of these compounds in disordered phases or in the initial stages of formation in paintings.

Milestone in the NTB phase investigation and beyond: direct insight into molecular self-assembly.

PubMed

Ivšić, Trpimir; Vinković, Marijana; Baumeister, Ute; Mikleušević, Ana; Lesac, Andreja

2014-12-14

Although liquid-crystalline materials are most widely exploited for flat-panel displays, their ability to self-organize into periodically ordered nanostructures gives rise to a broad variety of additional applications. The recently discovered low-temperature nematic phase (N(TB)) with unusual characteristics generated considerable attention within the scientific community: despite the fact that the molecules from which the phase is composed are not chiral, the helicoidal structure of the phase is strongly implicated. Here we report on combined experimental, computational and spectroscopic studies of the structural aspects influencing formation of the N(TB) phase as well as on the molecular organization within the phase. In an extensive DFT study, the structure-property prerequisite was traced to a "bent-propeller" shape of the molecule. We also demonstrate the first utilization of liquid state NMR for direct analysis of intermolecular interactions within thermotropic liquid-crystalline phases, providing new insight into molecular packing that can lead towards design of novel chiral functional materials. The synergy of experimental, computational and NMR studies suggests a syn-parallel helical molecular organization within the N(TB) phase.

Investigation and visualization of liquid-liquid flow in a vertically mounted Hele-Shaw cell: flow regimes, velocity and shape of droplets

NASA Astrophysics Data System (ADS)

Shad, S.; Gates, I. D.; Maini, B. B.

2009-11-01

The motion and shape of a liquid drop flowing within a continuous, conveying liquid phase in a vertical Hele-Shaw cell were investigated experimentally. The continuous phase was more viscous and wetted the bounding walls of the Hele-Shaw cell. The gap between the Hele-Shaw plates was set equal to 0.0226 cm. Four different flow regimes were observed: (a) small-droplet flow, (b) elongated-droplet flow, (c) churn flow and (d) channel flow. At low capillary number, that is, when capillary forces are larger than viscous forces, the droplet shape was irregular and changed with time and distance, and it moved with lower velocity than that of the conveying phase. At higher capillary number, several different shapes of stabilized elongated and flattened drops were observed. In contrast to gas-liquid systems, the velocities of droplets are higher than that of conveying liquid. New correlations derived from dimensionless analysis and fitted to the experimental data were generated to predict the elongated-drop velocity and aspect ratio.

Molecular differences between deuterated and protonated polystyrenes using reversed-phase high-performance liquid chromatography.

PubMed

Kayillo, Sindy; Gray, Michael J; Shalliker, R Andrew; Dennis, Gary R

2005-05-06

Isotopic substitution is a technique used to highlight particular bonds within a molecule for kinetic, spectroscopic and structure analysis. It is presumed that although some properties such as stretching frequencies will not be the same for substituted analogues, the chemical interactions will not vary appreciably as a function of labelling. Reversed-phase liquid chromatography has been used to demonstrate that there are significant differences between the chromatographic behaviour of a sequence of deuterated and protonated oligomeric polystyrenes. Two-dimensional reversed-phase liquid chromatography was used to show that even the diasteromers of the oligomers (n = 5) have retention mechanisms that are dependent on the subtle changes to the molecular conformation and electronic structure, which are a consequence of deuteration.

Measuring the expressed abundance of the three phases of water with an imaging spectrometer over melting snow

NASA Astrophysics Data System (ADS)

Green, Robert O.; Painter, Thomas H.; Roberts, Dar A.; Dozier, Jeff

2006-10-01

From imaging spectrometer data, we simultaneously estimate the abundance of the three phases of water in an environment that includes melting snow, basing the analysis on the spectral shift in the absorption coefficient between water vapor, liquid water, and ice at 940, 980, and 1030 nm respectively. We apply a spectral fitting algorithm that measures the expressed abundance of the three phases of water to a data set acquired by the Airborne Visible/Infrared Imaging Spectrometer (AVIRIS) over Mount Rainier, Washington, on 14 June 1996. Precipitable water vapor varies from 1 mm over the summit of Mount Rainier to 10 mm over the lower valleys to the northwest. Equivalent path absorption of liquid water varies from 0 to 13 mm, with the zero values over rocky areas and high-elevation snow and the high values associated with liquid water held in vegetation canopies and in melting snow. Ice abundance varies from 0 to 30 mm equivalent path absorption in the snow- and glacier-covered portions of Mount Rainier. The water and ice abundances are related to the amount of liquid water and the sizes of the ice grains in the near-surface layer. Precision of the estimates, calculated over locally homogeneous areas, indicates an uncertainty of better than 1.5% for all three phases, except for liquid water in vegetation, where an optimally homogeneous site was not found. The analysis supports new strategies for hydrological research and applications as imaging spectrometers become more available.

Advanced analytical techniques for the extraction and characterization of plant-derived essential oils by gas chromatography with mass spectrometry.

PubMed

Waseem, Rabia; Low, Kah Hin

2015-02-01

In recent years, essential oils have received a growing interest because of the positive health effects of their novel characteristics such as antibacterial, antifungal, and antioxidant activities. For the extraction of plant-derived essential oils, there is the need of advanced analytical techniques and innovative methodologies. An exhaustive study of hydrodistillation, supercritical fluid extraction, ultrasound- and microwave-assisted extraction, solid-phase microextraction, pressurized liquid extraction, pressurized hot water extraction, liquid-liquid extraction, liquid-phase microextraction, matrix solid-phase dispersion, and gas chromatography (one- and two-dimensional) hyphenated with mass spectrometry for the extraction through various plant species and analysis of essential oils has been provided in this review. Essential oils are composed of mainly terpenes and terpenoids with low-molecular-weight aromatic and aliphatic constituents that are particularly important for public health. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Investigation of Critical Burning of Fuel Droplets. [of liquid rocket propellant

NASA Technical Reports Server (NTRS)

Chanin, S. P.; Shearer, A. J.; Faeth, G. M.

1976-01-01

An earlier analysis for the combustion response of a liquid monopropellant strand (hydrazine) was extended to consider individual droplets and sprays. While small drops gave low or negative response, large droplets provided response near unity at low frequencies, with the response declining at frequencies greater than the characteristic liquid phase frequency. Temperature gradients in the liquid phase resulted in response peaks greater than unity. A second response peak was found for large drops which corresponded to gas phase transient effects. Spray response was generally reduced from the response of the largest injected droplet, however, even a small percentage of large droplets can yield appreciable response. An apparatus was designed and fabricated to allow observation of bipropellant fuel spray combustion at elevated pressures. A locally homogeneous model was developed to describe this combustion process which allows for high pressure phenomena associated with the thermodynamic critical point.

Performance of Liquid Phase Exfoliated Graphene As Electrochemical Double Layer Capacitors Electrodes

NASA Astrophysics Data System (ADS)

Huffstutler, Jacob; Wasala, Milinda; Richie, Julianna; Winchester, Andrew; Ghosh, Sujoy; Kar, Swastik; Talapatra, Saikat

2014-03-01

We will present the results of our investigations of electrochemical double layer capacitors (EDLCs) or supercapacitors (SC) fabricated using liquid-phase exfoliated graphene. Several electrolytes, such as aqueous potassium hydroxide KOH (6M), ionic 1-Butyl-3-methylimidazolium hexafluorophosphate [BMIM][PF6], and ionic 1-butyl-1-methylpyrrolidinium tris(pentafluoroethyl)trifluorophosphate[BMP][FAP] were used. These EDLC's show good performance compared to other carbon nanomaterials based EDLC's devices. We found that the liquid phase exfoliated graphene based devices possess specific capacitance values as high as 262 F/g, when used with ionic liquid electrolyte[BMP][FAP], with power densities (~ 454 W/kg) and energy densities (~ 0.38Wh/kg). Further, these devices indicated rapid charge transfer response even without the use of any binders or specially prepared current collectors. A detailed electrochemical impedance spectroscopy analysis in order to understand the phenomenon of charge storage in these materials will be presented.

Analysis of ecologically relevant pharmaceuticals in wastewater and surface water using selective solid phase extraction and UPLC/MS/MS

EPA Science Inventory

A rapid and sensitive method has been developed for the analysis of 48 human prescription active pharmaceutical ingredients (APIs) and 6 metabolites of interest, utilizing selective solid-phase extraction (SPE) and ultra performance liquid chromatography in combination with tripl...

Constant frequency pulsed phase-locked-loop instrument for measurement of ultrasonic velocity

NASA Technical Reports Server (NTRS)

Yost, William T.; Cantrell, John H.; Kushnick, Peter W.

1991-01-01

A new instrument based on a constant-frequency pulsed phase-locked-loop (CFPPLL) concept has been developed to accurately measure the ultrasonic wave velocity in liquids and changes in ultrasonic wave velocity in solids and liquids. An analysis of the system shows that it is immune to many of the frequency-dependent effects that plague other techniques. Measurements of the sound velocity in ultrapure water are used to confirm the analysis. The results are in excellent agreement with values from the literature, and establish that the CFPPLL provides a reliable, accurate way to measure velocities, as well as for monitoring small changes in velocity without the sensitivity to frequency-dependent phase shifts common to other measurement systems. The estimated sensitivity to phase changes is better than a few parts in 10 to the 7th.

Quality assessment of Herba Leonuri based on the analysis of multiple components using normal- and reversed-phase chromatographic methods.

PubMed

Dong, Shuya; He, Jiao; Hou, Huiping; Shuai, Yaping; Wang, Qi; Yang, Wenling; Sun, Zheng; Li, Qing; Bi, Kaishun; Liu, Ran

2017-12-01

A novel, improved, and comprehensive method for quality evaluation and discrimination of Herba Leonuri has been developed and validated based on normal- and reversed-phase chromatographic methods. To identify Herba Leonuri, normal- and reversed-phase high-performance thin-layer chromatography fingerprints were obtained by comparing the colors and R f values of the bands, and reversed-phase high-performance liquid chromatography fingerprints were obtained by using an Agilent Poroshell 120 SB-C18 within 28 min. By similarity analysis and hierarchical clustering analysis, we show that there are similar chromatographic patterns in Herba Leonuri samples, but significant differences in counterfeits and variants. To quantify the bio-active components of Herba Leonuri, reversed-phase high-performance liquid chromatography was performed to analyze syringate, leonurine, quercetin-3-O-robiniaglycoside, hyperoside, rutin, isoquercitrin, wogonin, and genkwanin simultaneously by single standard to determine multi-components method with rutin as internal standard. Meanwhile, normal-phase high-performance liquid chromatography was performed by using an Agilent ZORBAX HILIC Plus within 6 min to determine trigonelline and stachydrine using trigonelline as internal standard. Innovatively, among these compounds, bio-active components of quercetin-3-O-robiniaglycoside and trigonelline were first determined in Herba Leonuri. In general, the method integrating multi-chromatographic analyses offered an efficient way for the standardization and identification of Herba Leonuri. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Refusing to Twist: Demonstration of a Line Hexatic Phase in DNA Liquid Crystals

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

Strey, H. H.; NICHD/LPSB, National Institutes of Health, Building 12A/2041, Bethesda, Maryland 20892-5626; Wang, J.

2000-04-03

We report conclusive high resolution small angle x-ray scattering evidence that long DNA fragments form an untwisted line hexatic phase between the cholesteric and the crystalline phases. The line hexatic phase is a liquid-crystalline phase with long-range hexagonal bond-orientational order, long-range nematic order, but liquidlike, i.e., short-range, positional order. So far, it has not been seen in any other three dimensional system. By line-shape analysis of x-ray scattering data we found that positional order decreases when the line hexatic phase is compressed. We suggest that such anomalous behavior is a result of the chiral nature of DNA molecules. (c) 2000more » The American Physical Society.« less

Cavitation in liquid cryogens. 2: Hydrofoil

NASA Technical Reports Server (NTRS)

Hord, J.

1973-01-01

Boundary layer principles, along with two-phase concepts, are used to improve existing correlative theory for developed cavity data. Details concerning cavity instrumentation, data analysis, correlative techniques, and experimental and theoretical aspects of a cavitating hydrofoil are given. Both desinent and thermodynamic data, using liquid hydrogen and liquid nitrogen, are reported. The thermodynamic data indicated that stable thermodynamic equilibrium exists throughout the vaporous cryogen cavities. The improved correlative formulas were used to evaluate these data. A new correlating parameter based on consideration of mass limiting two-phase flow flux across the cavity interface, is proposed. This correlating parameter appears attractive for future correlative and predictive applications. Agreement between theory and experiment is discussed, and directions for future analysis are suggested. The front half of the cavities, developed on the hydrofoil, may be considered as parabolically shaped.

Skylab near-infrared observations of clouds indicating supercooled liquid water droplets

NASA Technical Reports Server (NTRS)

Curran, R. J.; Wu, M.-L. C.

1982-01-01

Orographically-induced lee-wave clouds were observed over New Mexico by a multichannel scanning radiometer on Skylab during December 1973. Channels centered at 0.83, 1.61 and 2.125 microns were used to determine the cloud optical thickness, thermodynamic phase and effective particle size. An additional channel centered at 11.4 microns was used to determine cloud-top temperature, which was corroborated through comparison with the stereographically determined cloud top altitudes and conventional temperature soundings. Analysis of the measured near-infrared reflection functions at 1.61 and 2.125 microns are most easily interpreted as indicating the presence of liquid-phase water droplets. This interpretation is not conclusive even after considerable effort to understand possible sources for misinterpretation. However, if accepted the resulting phase determination is considered anomalous due to the inferred cloud-top temperatures being in the -32 to -47 C range. Theory for the homogeneous nucleation of pure supercooled liquid water droplets predicts very short lifetimes for the liquid phase at these cold temperatures. A possible explanation for the observations is that the wave-clouds are composed of solution droplets. Impurities in the cloud droplets could decrease the homogeneous freezing rate for these droplets, permitting them to exist for a longer time in the liquid phase, at the cold temperatures found.

Formation, structure, and evolution of boiling nucleus and interfacial tension between bulk liquid phase and nucleus

NASA Astrophysics Data System (ADS)

Wang, Xiao-Dong; Peng, Xiao-Feng; Tian, Yong; Wang, Bu-Xuan

2005-05-01

In this paper, the concept of the molecular free path is introduced to derive a criterion distinguishing active molecules from inactive molecules in liquid phase. A concept of the critical aggregation concentration (CAC) of active molecules is proposed to describe the physical configuration before the formation of a nucleus during vapor-liquid phase transition. All active molecules exist as monomers when the concentration of active molecules is lower than CAC, while the active molecules will generate aggregation once the concentration of the active molecules reaches CAC. However, these aggregates with aggregation number, N, smaller than five can steadily exist in bulk phase. The other excess active molecules can only produce infinite aggregation and form a critical nucleus of vapor-liquid phase transition. Without any outer perturbation the state point of CAC corresponds to the critical superheated or supercooled state. Meanwhile, a model of two-region structure of a nucleus is proposed to describe nucleus evolution. The interfacial tension between bulk liquid phase and nucleus is dependent of the density gradient in the transition region and varies with the structure change of the transition region. With the interfacial tension calculated using this model, the predicted nucleation rate is very close to the experimental measurement. Furthermore, this model and associated analysis provides solid theoretical evidences to clarify the definition of nucleation rate and understand nucleation phenomenon with the insight into the physical nature.

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.

Determination of the Antibiotic Oxytetracycline in Commercial Milk by Solid-Phase Extraction: A High-Performance Liquid Chromatography (HPLC) Experiment for Quantitative Instrumental Analysis

ERIC Educational Resources Information Center

Mei-Ratliff, Yuan

2012-01-01

Trace levels of oxytetracylcine spiked into commercial milk samples are extracted, cleaned up, and preconcentrated using a C[subscript 18] solid-phase extraction column. The extract is then analyzed by a high-performance liquid chromatography (HPLC) instrument equipped with a UV detector and a C[subscript 18] column (150 mm x 4.6 mm x 3.5 [mu]m).…

Artifact-free dynamic atomic force microscopy reveals monotonic dissipation for a simple confined liquid

NASA Astrophysics Data System (ADS)

Kaggwa, G. B.; Kilpatrick, J. I.; Sader, J. E.; Jarvis, S. P.

2008-07-01

We present definitive interaction measurements of a simple confined liquid (octamethylcyclotetrasiloxane) using artifact-free frequency modulation atomic force microscopy. We use existing theory to decouple the conservative and dissipative components of the interaction, for a known phase offset from resonance (90° phase shift), that has been deliberately introduced into the experiment. Further we show the qualitative influence on the conservative and dissipative components of the interaction of a phase error deliberately introduced into the measurement, highlighting that artifacts, such as oscillatory dissipation, can be readily observed when the phase error is not compensated for in the force analysis.

Stochastical analysis of surfactant-enhanced remediation of denser-than-water nonaqueous phase liquid (DNAPL)-contaminated soils.

PubMed

Zhang, Renduo; Wood, A Lynn; Enfield, Carl G; Jeong, Seung-Woo

2003-01-01

Stochastical analysis was performed to assess the effect of soil spatial variability and heterogeneity on the recovery of denser-than-water nonaqueous phase liquids (DNAPL) during the process of surfactant-enhanced remediation. UTCHEM, a three-dimensional, multicomponent, multiphase, compositional model, was used to simulate water flow and chemical transport processes in heterogeneous soils. Soil spatial variability and heterogeneity were accounted for by considering the soil permeability as a spatial random variable and a geostatistical method was used to generate random distributions of the permeability. The randomly generated permeability fields were incorporated into UTCHEM to simulate DNAPL transport in heterogeneous media and stochastical analysis was conducted based on the simulated results. From the analysis, an exponential relationship between average DNAPL recovery and soil heterogeneity (defined as the standard deviation of log of permeability) was established with a coefficient of determination (r2) of 0.991, which indicated that DNAPL recovery decreased exponentially with increasing soil heterogeneity. Temporal and spatial distributions of relative saturations in the water phase, DNAPL, and microemulsion in heterogeneous soils were compared with those in homogeneous soils and related to soil heterogeneity. Cleanup time and uncertainty to determine DNAPL distributions in heterogeneous soils were also quantified. The study would provide useful information to design strategies for the characterization and remediation of nonaqueous phase liquid-contaminated soils with spatial variability and heterogeneity.

Analysis of space tug operating techniques. Volume 2: Study results

NASA Technical Reports Server (NTRS)

1972-01-01

The design requirements for space tug systems and cost analysis of the refurbishment phases are discussed. The vehicle is an integral propulsion stage using liquid hydrogen and liquid oxygen as propellants and is capable of operating either as a fully or a partially autonomous vehicle. Structural features are an integral liquid hydrogen tank, a liquid oxygen tank, a meteoroid shield, an aft conical docking and structural support ring, and a staged combustion main engine. The vehicle is constructed of major modules for ease of maintenance. Line drawings and block diagrams are included to explain the maintenance requirements for the subsystems.

Hollow-fiber liquid-phase microextraction coupled with miniature capillary electrophoresis for the trace analysis of four aliphatic aldehydes in water samples.

PubMed

Li, Ying; Yi, Fan; Zheng, Yiliang; Wang, Yu; Ye, Jiannong; Chu, Qingcui

2015-08-01

An environmentally friendly method for the trace analysis of four aliphatic aldehydes as water disinfection byproducts has been developed based on hollow-fiber liquid-phase microextraction followed by miniature capillary electrophoresis with amperometric detection. After derivatization with 2-thiobarbituric acid, four aliphatic aldehydes (formaldehyde, acetaldehyde, propylaldehyde, and butyraldehyde) became detectable by the amperometric detector. Under the optimum conditions, four aliphatic aldehydes can be well separated from the coexisting interferents as well as their homologs (pentanal, glyoxal, and methyl-glyoxal), and the limits of detection (S/N = 3) could reach sub-nanogram-per-milliliter level based on hollow-fiber liquid-phase microextraction. The proposed method has been applied for the analyses of above four aliphatic aldehydes in different water samples such as drinking water, tap water, and river water, and the average recoveries were in the range of 90-113%, providing an alternative to conventional and microchip capillary electrophoresis approaches. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

[The progress in speciation analysis of trace elements by atomic spectrometry].

PubMed

Wang, Zeng-Huan; Wang, Xu-Nuo; Ke, Chang-Liang; Lin, Qin

2013-12-01

The main purpose of the present work is to review the different non-chromatographic methods for the speciation analysis of trace elements in geological, environmental, biological and medical areas. In this paper, the sample processing methods in speciation analysis were summarized, and the main strategies for non-chromatographic technique were evaluated. The basic principles of the liquid extractions proposed in the published literatures recently and their advantages and disadvantages were discussed, such as conventional solvent extraction, cloud point extraction, single droplet microextraction, and dispersive liquid-liquid microextraction. Solid phase extraction, as a non-chromatographic technique for speciation analysis, can be used in batch or in flow detection, and especially suitable for the online connection to atomic spectrometric detector. The developments and applications of sorbent materials filled in the columns of solid phase extraction were reviewed. The sorbents include chelating resins, nanometer materials, molecular and ion imprinted materials, and bio-sorbents. Other techniques, e. g. hydride generation technique and coprecipitation, were also reviewed together with their main applications.

Analysis of a gas-liquid film plasma reactor for organic compound oxidation.

PubMed

Hsieh, Kevin; Wang, Huijuan; Locke, Bruce R

2016-11-05

A pulsed electrical discharge plasma formed in a tubular reactor with flowing argon carrier gas and a liquid water film was analyzed using methylene blue as a liquid phase hydroxyl radical scavenger and simultaneous measurements of hydrogen peroxide formation. The effects of liquid flow rate, liquid conductivity, concentration of dye, and the addition of ferrous ion on dye decoloration and degradation were determined. Higher liquid flow rates and concentrations of dye resulted in less decoloration percentages and hydrogen peroxide formation due to initial liquid conductivity effects and lower residence times in the reactor. The highest decoloration energy yield of dye found in these studies was 5.2g/kWh when using the higher liquid flow rate and adding the catalyst. The non-homogeneous nature of the plasma discharge favors the production of hydrogen peroxide in the plasma-liquid interface over the chemical oxidation of the organic in the bulk liquid phase and post-plasma reactions with the Fenton catalyst lead to complete utilization of the plasma-formed hydrogen peroxide. Copyright © 2016 Elsevier B.V. All rights reserved.

Liquid Crystals in Chromatography

NASA Astrophysics Data System (ADS)

Witkiewicz, Zygfryd

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

Membrane Bending Moduli of Coexisting Liquid Phases Containing Transmembrane Peptide.

PubMed

Usery, Rebecca D; Enoki, Thais A; Wickramasinghe, Sanjula P; Nguyen, V P; Ackerman, David G; Greathouse, Denise V; Koeppe, Roger E; Barrera, Francisco N; Feigenson, Gerald W

2018-05-08

A number of highly curved membranes in vivo, such as epithelial cell microvilli, have the relatively high sphingolipid content associated with "raft-like" composition. Given the much lower bending energy measured for bilayers with "nonraft" low sphingomyelin and low cholesterol content, observing high curvature for presumably more rigid compositions seems counterintuitive. To understand this behavior, we measured membrane rigidity by fluctuation analysis of giant unilamellar vesicles. We found that including a transmembrane helical GWALP peptide increases the membrane bending modulus of the liquid-disordered (Ld) phase. We observed this increase at both low-cholesterol fraction and higher, more physiological cholesterol fraction. We find that simplified, commonly used Ld and liquid-ordered (Lo) phases are not representative of those that coexist. When Ld and Lo phases coexist, GWALP peptide favors the Ld phase with a partition coefficient of 3-10 depending on mixture composition. In model membranes at high cholesterol fractions, Ld phases with GWALP have greater bending moduli than the Lo phase that would coexist. Copyright © 2018 Biophysical Society. Published by Elsevier Inc. All rights reserved.

NMR signal analysis to attribute the components to the solid/liquid phases present in mixes and ice creams.

PubMed

Mariette, François; Lucas, Tiphaine

2005-03-09

The NMR relaxation signals from complex products such as ice cream are hard to interpret because of the multiexponential behavior of the relaxation signal and the difficulty of attributing the NMR relaxation components to specific molecule fractions. An attribution of the NMR relaxation parameters is proposed, however, based on an approach that combines quantitative analysis of the spin-spin and spin-lattice relaxation times and the signal intensities with characterization of the ice cream components. We have been able to show that NMR can be used to describe the crystallized and liquid phases separately. The first component of the spin-spin and spin-lattice relaxation describes the behavior of the protons of the crystallized fat in the mix. The amount of fat crystals can then be estimated. In the case of ice cream, only the spin-lattice relaxation signal from the crystallized fraction is relevant. However, it enables the ice protons and the protons of the crystallized fat to be distinguished. The spin-lattice relaxation time can be used to describe the mobility of the protons in the different crystallized phases and also to quantify the amount of ice crystals and fat crystals in the ice cream. The NMR relaxation of the liquid phase of the mix has a biexponential behavior. A first component is attributable to the liquid fraction of the fat and to the sugars, while a second component is attributable to the aqueous phase. Overall, the study shows that despite the complexity of the NMR signal from ice cream, a number of relevant parameters can be extracted to study the influence of the formulation and of the process stages on the ice fraction, the crystallized fat fraction, and the liquid aqueous fraction.

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.

Porous Graphitic Carbon Liquid Chromatography-Mass Spectrometry Analysis of Drought Stress-Responsive Raffinose Family Oligosaccharides in Plant Tissues.

PubMed

Jorge, Tiago F; Florêncio, Maria H; António, Carla

2017-01-01

Drought is a major limiting factor in agriculture and responsible for dramatic crop yield losses worldwide. The adjustment of the metabolic status via accumulation of drought stress-responsive osmolytes is one of the many strategies that some plants have developed to cope with water deficit conditions. Osmolytes are highly polar compounds, analysis of whcih is difficult with typical reversed-phase chromatography. Porous graphitic carbon (PGC) has shown to be a suitable alternative to reversed-phase stationary phases for the analysis of highly polar compounds typically found in the plant metabolome. In this chapter, we describe the development and validation of a PGC-based liquid chromatography tandem mass spectrometry (LC-MS n ) method suitable for the target analysis of water-soluble carbohydrates, such as raffinose family oligosaccharides (RFOs). We present detailed information regarding PGC column equilibration, LC-MS n system operation, data analysis, and important notes to be considered during the steps of method development and validation.

New approaches to the analysis of complex samples using fluorescence lifetime techniques and organized media

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

Hertz, P.R.

Fluorescence spectroscopy is a highly sensitive and selective tool for the analysis of complex systems. In order to investigate the efficacy of several steady state and dynamic techniques for the analysis of complex systems, this work focuses on two types of complex, multicomponent samples: petrolatums and coal liquids. It is shown in these studies dynamic, fluorescence lifetime-based measurements provide enhanced discrimination between complex petrolatum samples. Additionally, improved quantitative analysis of multicomponent systems is demonstrated via incorporation of organized media in coal liquid samples. This research provides the first systematic studies of (1) multifrequency phase-resolved fluorescence spectroscopy for dynamic fluorescence spectralmore » fingerprinting of complex samples, and (2) the incorporation of bile salt micellar media to improve accuracy and sensitivity for characterization of complex systems. In the petroleum studies, phase-resolved fluorescence spectroscopy is used to combine spectral and lifetime information through the measurement of phase-resolved fluorescence intensity. The intensity is collected as a function of excitation and emission wavelengths, angular modulation frequency, and detector phase angle. This multidimensional information enhances the ability to distinguish between complex samples with similar spectral characteristics. Examination of the eigenvalues and eigenvectors from factor analysis of phase-resolved and steady state excitation-emission matrices, using chemometric methods of data analysis, confirms that phase-resolved fluorescence techniques offer improved discrimination between complex samples as compared with conventional steady state methods.« less

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.

Non‐Thermal Plasma in Contact with Water: The Origin of Species

PubMed Central

Gorbanev, Yury

2016-01-01

Abstract Non‐thermal atmospheric pressure plasma has attracted considerable attention in recent years due to its potential for biomedical applications. Determining the mechanism of the formation of reactive species in liquid treated with plasma is thus of paramount importance for both fundamental and applied research. In this work, the origin of reactive species in plasma‐treated aqueous solutions was investigated by using spin‐trapping, hydrogen and oxygen isotopic labelling and electron paramagnetic resonance (EPR) spectroscopy. The species originating from molecules in the liquid phase and those introduced with the feed gas were differentiated by EPR and 1H NMR analysis of liquid samples. The effects of water vapour and oxygen admixtures in the feed gas were investigated. All the reactive species detected in the liquid samples were shown to be formed largely in the plasma gas phase. It is suggested that hydrogen peroxide (determined by UV/Vis analysis) is formed primarily in the plasma tube, whereas the radical species ⋅OOH, ⋅OH and ⋅H are proposed to originate from the region between the plasma nozzle and the liquid sample. PMID:26833560

Electrorotation of colloidal particles in liquid crystals

NASA Astrophysics Data System (ADS)

Liao, G.; Smalyukh, I. I.; Kelly, J. R.; Lavrentovich, O. D.; Jákli, A.

2005-09-01

We present the first observations of dc electric-field-induced rotational motion of finite particles in liquid crystals. We show that the electrorotation is essentially identical to the well-known Quincke rotation, which in liquid crystals triggers an additional translational motion at higher fields. In the smectic phase the translational motion is confined to the two-dimensional geometry of smectic layers, in contrast to the isotropic and nematic phases, where the particles can move in all three dimensions. We demonstrate that by a proper analysis of the electrorotation, one can determine the in-plane viscosity of smectic liquid crystals. This method needs only a small amount of material, does not require uniform alignment over large areas, and enables probing rheological properties locally.

[Corrected Title: Solid-Phase Extraction of Polar Compounds from Water] Automated Electrostatics Environmental Chamber

NASA Technical Reports Server (NTRS)

Sauer, Richard; Rutz, Jeffrey; Schultz, John

2005-01-01

A solid-phase extraction (SPE) process has been developed for removing alcohols, carboxylic acids, aldehydes, ketones, amines, and other polar organic compounds from water. This process can be either a subprocess of a water-reclamation process or a means of extracting organic compounds from water samples for gas-chromatographic analysis. This SPE process is an attractive alternative to an Environmental Protection Administration liquid-liquid extraction process that generates some pollution and does not work in a microgravitational environment. In this SPE process, one forces a water sample through a resin bed by use of positive pressure on the upstream side and/or suction on the downstream side, thereby causing organic compounds from the water to be adsorbed onto the resin. If gas-chromatographic analysis is to be done, the resin is dried by use of a suitable gas, then the adsorbed compounds are extracted from the resin by use of a solvent. Unlike the liquid-liquid process, the SPE process works in both microgravity and Earth gravity. In comparison with the liquid-liquid process, the SPE process is more efficient, extracts a wider range of organic compounds, generates less pollution, and costs less.

Solid-phase extraction in combination with dispersive liquid-liquid microextraction and ultra-high performance liquid chromatography-tandem mass spectrometry analysis: the ultra-trace determination of 10 antibiotics in water samples.

PubMed

Liang, Ning; Huang, Peiting; Hou, Xiaohong; Li, Zhen; Tao, Lei; Zhao, Longshan

2016-02-01

A novel method, solid-phase extraction combined with dispersive liquid-liquid microextraction (SPE-DLLME), was developed for ultra-preconcentration of 10 antibiotics in different environmental water samples prior to ultra-high performance liquid chromatography-tandem mass spectrometry detection. The optimized results were obtained as follows: after being adjusted to pH 4.0, the water sample was firstly passed through PEP-2 column at 10 mL min(-1), and then methanol was used to elute the target analytes for the following steps. Dichloromethane was selected as extraction solvent, and methanol/acetonitrile (1:1, v/v) as dispersive solvent. Under optimal conditions, the calibration curves were linear in the range of 1-1000 ng mL(-1) (sulfamethoxazole, cefuroxime axetil), 5-1000 ng mL(-1) (tinidazole), 10-1000 ng mL(-1) (chloramphenicol), 2-1000 ng mL(-1) (levofloxacin oxytetracycline, doxycycline, tetracycline, and ciprofloxacin) and 1-400 ng mL(-1) (sulfadiazine) with a good precision. The LOD and LOQ of the method were at very low levels, below 1.67 and 5.57 ng mL(-1), respectively. The relative recoveries of the target analytes were in the range from 64.16% to 99.80% with relative standard deviations between 0.7 and 8.4%. The matrix effect of this method showed a great decrease compared with solid-phase extraction and a significant value of enrichment factor (EF) compared with dispersive liquid-liquid microextraction. The developed method was successfully applied to the extraction and analysis of antibiotics in different water samples with satisfactory results.

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.

Determination of tetraalkyllead compounds in gasoline by liquid chromatography-atomic absorption spectrometry

USGS Publications Warehouse

Messman, J.D.; Rains, T.C.

1981-01-01

A liquid chromatography-atomic absorption spectrometry (LC-AAS) hybrid analytical technique is presented for metal speciation measurements on complex liquid samples. The versatility and inherent metal selectivity of the technique are Illustrated by the rapid determination of five tetraalkyllead compounds in commercial gasoline. Separation of the individual tetraalkyllead species is achieved by reversed-phase liquid chromatography using an acetonitrile/water mobile phase. The effluent from the liquid Chromatograph Is introduced directly into the aspiration uptake capillary of the nebulizer of an air/acetylene flame atomic absorption spectrometer. Spectral interferences due to coeluting hydrocarbon matrix constituents were not observed at the 283.3-nm resonance line of lead used for analysis. Detection limits of this LC-AAS hydrid analytical technique, based on a 20-??L injection, are approximately 10 ng Pb for each tetraalkyllead compound.

Prospects for the application of radiometric methods in the measurement of two-phase flows

NASA Astrophysics Data System (ADS)

Zych, Marcin

2018-06-01

The article constitutes an overview of the application of radiometric methods in the research of two-phase flows: liquid-solid particles and liquid-gas flows. The methods which were used were described on the basis of the experiments which were conducted in the Water Laboratory of the Wrocław University of Environmental and Life Sciences and in the Sedimentological Laboratory of the Faculty of Geology, Geophysics and Environmental Protection, AGH-UST in Kraków. The advanced mathematical methods for the analysis of signals from scintillation probes that were applied enable the acquisition of a number of parameters associated with the flowing two-phase mixture, such as: average velocities of the particular phases, concentration of the solid phase, and void fraction for a liquid-gas mixture. Despite the fact that the application of radioactive sources requires considerable carefulness and a number of state permits, in many cases these sources become useful in the experiments which are presented.

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.

Interfacial nonequilibrium and Bénard-Marangoni instability of a liquid-vapor system

NASA Astrophysics Data System (ADS)

Margerit, J.; Colinet, P.; Lebon, G.; Iorio, C. S.; Legros, J. C.

2003-10-01

We study Bénard-Marangoni instability in a system formed by a horizontal liquid layer and its overlying vapor. The liquid is lying on a hot rigid plate and the vapor is bounded by a cold parallel plate. A pump maintains a reduced pressure in the vapor layer and evacuates the vapor. This investigation is undertaken within the classical quasisteady approximation for both the vapor and the liquid phases. The two layers are separated by a deformable interface. Temporarily frozen temperature and velocity distributions are employed at each instant for the stability analysis, limited to infinitesimal disturbances (linear regime). We use irreversible thermodynamics to model the phase change under interfacial nonequilibrium. Within this description, the interface appears as a barrier for transport of both heat and mass. Hence, in contrast with previous studies, we consider the possibility of a temperature jump across the interface, as recently measured experimentally. The stability analysis shows that the interfacial resistances to heat and mass transfer have a destabilizing influence compared to an interface that is in thermodynamic equilibrium. The role of the fluctuations in the vapor phase on the onset of instability is discussed. The conditions to reduce the system to a one phase model are also established. Finally, the influence of the evaporation parameters and of the presence of an inert gas on the marginal stability curves is discussed.

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.

Simultaneous determination of ascorbic acid and caffeine in commercial soft drinks using reversed-phase ultraperformance liquid chromatography.

PubMed

Turak, Fatma; Güzel, Remziye; Dinç, Erdal

2017-04-01

A new reversed-phase ultraperformance liquid chromatography method with a photodiode array detector was developed for the quantification of ascorbic acid (AA) and caffeine (CAF) in 11 different commercial drinks consisting of one energy drink and 10 ice tea drinks. Separation of the analyzed AA and CAF with an internal standard, caffeic acid, was performed on a Waters BEH C 18 column (100 mm × 2.1 mm, 1.7 μm i.d.), using a mobile phase consisting of acetonitrile and 0.2M H 3 PO 4 (11:89, v/v) with a flow rate of 0.25 mL/min and an injection volume of 1.0 μL. Calibration graphs for AA and CAF were computed from the peak area ratio of AA/internal standard and CAF/internal standard detected at 244.0 nm and 273.6 nm, respectively. The developed reversed-phase ultraperformance liquid chromatography method was validated by analyzing standard addition samples. The proposed reversed-phase ultraperformance liquid chromatography method gave us successful results for the quantitative analysis of commercial drinks containing AA and CAF substances. Copyright © 2016. Published by Elsevier B.V.

Liquid phase evaporation on the normal shock wave in moist air transonic flows in nozzles

NASA Astrophysics Data System (ADS)

Dykas, Sławomir; Szymański, Artur; Majkut, Mirosław

2017-06-01

This paper presents a numerical analysis of the atmospheric air transonic flow through de Laval nozzles. By nature, atmospheric air always contains a certain amount of water vapor. The calculations were made using a Laval nozzle with a high expansion rate and a convergent-divergent (CD) "half-nozzle", referred to as a transonic diffuser, with a much slower expansion rate. The calculations were performed using an in-house CFD code. The computational model made it possible to simulate the formation of the liquid phase due to spontaneous condensation of water vapor contained in moist air. The transonic flow calculations also take account of the presence of a normal shock wave in the nozzle supersonic part to analyze the effect of the liquid phase evaporation.

CFD analysis of laboratory scale phase equilibrium cell operation

NASA Astrophysics Data System (ADS)

Jama, Mohamed Ali; Nikiforow, Kaj; Qureshi, Muhammad Saad; Alopaeus, Ville

2017-10-01

For the modeling of multiphase chemical reactors or separation processes, it is essential to predict accurately chemical equilibrium data, such as vapor-liquid or liquid-liquid equilibria [M. Šoóš et al., Chem. Eng. Process.: Process Intensif. 42(4), 273-284 (2003)]. The instruments used in these experiments are typically designed based on previous experiences, and their operation verified based on known equilibria of standard components. However, mass transfer limitations with different chemical systems may be very different, potentially falsifying the measured equilibrium compositions. In this work, computational fluid dynamics is utilized to design and analyze laboratory scale experimental gas-liquid equilibrium cell for the first time to augment the traditional analysis based on plug flow assumption. Two-phase dilutor cell, used for measuring limiting activity coefficients at infinite dilution, is used as a test case for the analysis. The Lagrangian discrete model is used to track each bubble and to study the residence time distribution of the carrier gas bubbles in the dilutor cell. This analysis is necessary to assess whether the gas leaving the cell is in equilibrium with the liquid, as required in traditional analysis of such apparatus. Mass transfer for six different bio-oil compounds is calculated to determine the approach equilibrium concentration. Also, residence times assuming plug flow and ideal mixing are used as reference cases to evaluate the influence of mixing on the approach to equilibrium in the dilutor. Results show that the model can be used to predict the dilutor operating conditions for which each of the studied gas-liquid systems reaches equilibrium.

CFD analysis of laboratory scale phase equilibrium cell operation.

PubMed

Jama, Mohamed Ali; Nikiforow, Kaj; Qureshi, Muhammad Saad; Alopaeus, Ville

2017-10-01

For the modeling of multiphase chemical reactors or separation processes, it is essential to predict accurately chemical equilibrium data, such as vapor-liquid or liquid-liquid equilibria [M. Šoóš et al., Chem. Eng. Process Intensif. 42(4), 273-284 (2003)]. The instruments used in these experiments are typically designed based on previous experiences, and their operation verified based on known equilibria of standard components. However, mass transfer limitations with different chemical systems may be very different, potentially falsifying the measured equilibrium compositions. In this work, computational fluid dynamics is utilized to design and analyze laboratory scale experimental gas-liquid equilibrium cell for the first time to augment the traditional analysis based on plug flow assumption. Two-phase dilutor cell, used for measuring limiting activity coefficients at infinite dilution, is used as a test case for the analysis. The Lagrangian discrete model is used to track each bubble and to study the residence time distribution of the carrier gas bubbles in the dilutor cell. This analysis is necessary to assess whether the gas leaving the cell is in equilibrium with the liquid, as required in traditional analysis of such apparatus. Mass transfer for six different bio-oil compounds is calculated to determine the approach equilibrium concentration. Also, residence times assuming plug flow and ideal mixing are used as reference cases to evaluate the influence of mixing on the approach to equilibrium in the dilutor. Results show that the model can be used to predict the dilutor operating conditions for which each of the studied gas-liquid systems reaches equilibrium.

A versatile in situ spectroscopic cell for fluorescence/transmission EXAFS and X-ray diffraction of heterogeneous catalysts in gas and liquid phase.

PubMed

Hannemann, Stefan; Casapu, Maria; Grunwaldt, Jan Dierk; Haider, Peter; Trüssel, Philippe; Baiker, Alfons; Welter, Edmund

2007-07-01

A new spectroscopic cell suitable for the analysis of heterogeneous catalysts by fluorescence EXAFS (extended X-ray absorption fine structure), transmission EXAFS and X-ray diffraction during in situ treatments and during catalysis is described. Both gas-phase and liquid-phase reactions can be investigated combined with on-line product analysis performed either by mass spectrometry or infrared spectroscopy. The set-up allows measurements from liquid-nitrogen temperature to 973 K. The catalysts are loaded preferentially as powders, but also as self-supporting wafers. The reaction cell was tested in various case studies demonstrating its flexibility and its wide applicability from model studies at liquid-nitrogen temperature to operando studies under realistic reaction conditions. Examples include structural studies during (i) the reduction of alumina-supported noble metal particles prepared by flame-spray pyrolysis and analysis of alloying in bimetallic noble metal particles (0.1%Pt-0.1%Pd/Al(2)O(3), 0.1%Pt-0.1%Ru/Al(2)O(3), 0.1%Pt-0.1%Rh/Al(2)O(3), 0.1%Au-0.1%Pd/Al(2)O(3)), (ii) reactivation of aged 0.8%Pt-16%BaO-CeO(2) NO(x) storage-reduction catalysts including the NO(x) storage/reduction cycle, and (iii) alcohol oxidation over gold catalysts (0.6%Au-20%CuO-CeO(2)).

Method for preconcentrating a sample for subsequent analysis

DOEpatents

Zaromb, Solomon

1990-01-01

A system for analysis of trace concentration of contaminants in air includes a portable liquid chromatograph and a preconcentrator for the contaminants to be analyzed. The preconcentrator includes a sample bag having an inlet valve and an outlet valve for collecting an air sample. When the sample is collected the sample bag is connected in series with a sorbing apparatus in a recirculation loop. The sorbing apparatus has an inner gas-permeable container containing a sorbent material and an outer gas-impermeable container. The sample is circulated through the outer container and around the inner container for trapping and preconcentrating the contaminants in the sorbent material. The sorbent material may be a liquid having the same composition as the mobile phase of the chromatograph for direct injection thereinto. Alternatively, the sorbent material may be a porous, solid body, to which mobile phase liquid is added after preconcentration of the contaminants for dissolving the contaminants, the liquid solution then being withdrawn for injection into the chromatograph.

Interactions in the ionic liquid [EMIM][FAP]: a coupled experimental and computational analysis.

PubMed

Voroshylova, Iuliia V; Teixeira, Filipe; Costa, Renata; Pereira, Carlos M; Cordeiro, M Natália D S

2016-01-28

Gas-phase electronic and structural properties of the room temperature ionic liquid 1-ethyl-3-methylimidazolium tris(perfluoroethyl)trifluorophosphate ([EMIM][FAP]) were studied using density functional theory, and confirmed with results from infrared spectroscopy. A conformational analysis allowed the identification of several plausible conformers of the ion pairs. For the detected conformers, the infrared spectra were predicted and their thermodynamic properties were evaluated. The topology of the electronic density of the most stable conformers of [EMIM][FAP] ion pairs were characterised using the quantum theory of atoms in molecules. A number of possible hydrogen bonds between the cations and anions of the ionic liquid were identified. Excellent correspondence was found between the predicted spectra of gas-phase [EMIM][FAP] conformers and the experimental infrared spectrum, which in turn allowed a clear attribution of the vibration modes of [EMIM][FAP]. Finally, the contribution of the various conformers of both isomers of the [FAP](-) anion to the ionic liquid macro-properties is shown.

Simple setup for gas-phase H/D exchange mass spectrometry coupled to electron transfer dissociation and ion mobility for analysis of polypeptide structure on a liquid chromatographic time scale.

PubMed

Mistarz, Ulrik H; Brown, Jeffery M; Haselmann, Kim F; Rand, Kasper D

2014-12-02

Gas-phase hydrogen/deuterium exchange (HDX) is a fast and sensitive, yet unharnessed analytical approach for providing information on the structural properties of biomolecules, in a complementary manner to mass analysis. Here, we describe a simple setup for ND3-mediated millisecond gas-phase HDX inside a mass spectrometer immediately after ESI (gas-phase HDX-MS) and show utility for studying the primary and higher-order structure of peptides and proteins. HDX was achieved by passing N2-gas through a container filled with aqueous deuterated ammonia reagent (ND3/D2O) and admitting the saturated gas immediately upstream or downstream of the primary skimmer cone. The approach was implemented on three commercially available mass spectrometers and required no or minor fully reversible reconfiguration of gas-inlets of the ion source. Results from gas-phase HDX-MS of peptides using the aqueous ND3/D2O as HDX reagent indicate that labeling is facilitated exclusively through gaseous ND3, yielding similar results to the infusion of purified ND3-gas, while circumventing the complications associated with the use of hazardous purified gases. Comparison of the solution-phase- and gas-phase deuterium uptake of Leu-Enkephalin and Glu-Fibrinopeptide B, confirmed that this gas-phase HDX-MS approach allows for labeling of sites (heteroatom-bound non-amide hydrogens located on side-chains, N-terminus and C-terminus) not accessed by classical solution-phase HDX-MS. The simple setup is compatible with liquid chromatography and a chip-based automated nanoESI interface, allowing for online gas-phase HDX-MS analysis of peptides and proteins separated on a liquid chromatographic time scale at increased throughput. Furthermore, online gas-phase HDX-MS could be performed in tandem with ion mobility separation or electron transfer dissociation, thus enabling multiple orthogonal analyses of the structural properties of peptides and proteins in a single automated LC-MS workflow.

Simultaneous analysis for water- and fat-soluble vitamins by a novel single chromatography technique unifying supercritical fluid chromatography and liquid chromatography.

PubMed

Taguchi, Kaori; Fukusaki, Eiichiro; Bamba, Takeshi

2014-10-03

Chromatography techniques usually use a single state in the mobile phase, such as liquid, gas, or supercritical fluid. Chromatographers manage one of these techniques for their purpose but are sometimes required to use multiple methods, or even worse, multiple techniques when the target compounds have a wide range of chemical properties. To overcome this challenge, we developed a single method covering a diverse compound range by means of a "unified" chromatography which completely bridges supercritical fluid chromatography and liquid chromatography. In our method, the phase state was continuously changed in the following order; supercritical, subcritical and liquid. Moreover, the gradient of the mobile phase starting at almost 100% CO2 was replaced with 100% methanol at the end completely. As a result, this approach achieved further extension of the polarity range of the mobile phase in a single run, and successfully enabled the simultaneous analysis of fat- and water-soluble vitamins with a wide logP range of -2.11 to 10.12. Furthermore, the 17 vitamins were exceptionally separated in 4min. Our results indicated that the use of dense CO2 and the replacement of CO2 by methanol are practical approaches in unified chromatography covering diverse compounds. Additionally, this is a first report to apply the novel approach to unified chromatography, and can open another door for diverse compound analysis in a single chromatographic technique with single injection, single column and single system. Copyright © 2014. Published by Elsevier B.V.

Improving Mixed-phase Cloud Parameterization in Climate Model with the ACRF Measurements

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

Wang, Zhien

Mixed-phase cloud microphysical and dynamical processes are still poorly understood, and their representation in GCMs is a major source of uncertainties in overall cloud feedback in GCMs. Thus improving mixed-phase cloud parameterizations in climate models is critical to reducing the climate forecast uncertainties. This study aims at providing improved knowledge of mixed-phase cloud properties from the long-term ACRF observations and improving mixed-phase clouds simulations in the NCAR Community Atmosphere Model version 5 (CAM5). The key accomplishments are: 1) An improved retrieval algorithm was developed to provide liquid droplet concentration for drizzling or mixed-phase stratiform clouds. 2) A new ice concentrationmore » retrieval algorithm for stratiform mixed-phase clouds was developed. 3) A strong seasonal aerosol impact on ice generation in Arctic mixed-phase clouds was identified, which is mainly attributed to the high dust occurrence during the spring season. 4) A suite of multi-senor algorithms was applied to long-term ARM observations at the Barrow site to provide a complete dataset (LWC and effective radius profile for liquid phase, and IWC, Dge profiles and ice concentration for ice phase) to characterize Arctic stratiform mixed-phase clouds. This multi-year stratiform mixed-phase cloud dataset provides necessary information to study related processes, evaluate model stratiform mixed-phase cloud simulations, and improve model stratiform mixed-phase cloud parameterization. 5). A new in situ data analysis method was developed to quantify liquid mass partition in convective mixed-phase clouds. For the first time, we reliably compared liquid mass partitions in stratiform and convective mixed-phase clouds. Due to the different dynamics in stratiform and convective mixed-phase clouds, the temperature dependencies of liquid mass partitions are significantly different due to much higher ice concentrations in convective mixed phase clouds. 6) Systematic evaluations of mixed-phase cloud simulations by CAM5 were performed. Measurement results indicate that ice concentrations control stratiform mixed-phase cloud properties. The improvement of ice concentration parameterization in the CAM5 was done in close collaboration with Dr. Xiaohong Liu, PNNL (now at University of Wyoming).« less

Analysis of lignans in Magnoliae Flos by turbulent flow chromatography with online solid-phase extraction and high-performance liquid chromatography with tandem mass spectrometry.

PubMed

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

2016-04-01

In this study, a method coupling turbulent flow chromatography with online solid-phase extraction and high-performance liquid chromatography with tandem mass spectrometry was developed for analyzing the lignans in Magnoliae Flos. By the online pretreatment of turbulent flow chromatography solid-phase extraction, the impurities removal and analytes concentration were automatically processed, and the lignans were separated rapidly and well. Seven lignans of Magnoliae Flos including epieudesmin, magnolin, 1-irioresinol-B-dimethyl ether, epi-magnolin, fargesin aschantin, and demethoxyaschantin were identified by comparing their retention behavior, UV spectra, and mass spectra with those of reference substances or literature data. The developed method was validated, and the good results showed that the method was not only automatic and rapid, but also accurate and reliable. The turbulent flow chromatography with online solid-phase extraction and high-performance liquid chromatography with tandem mass spectrometry method holds a high potential to become an effective method for the quality control of lignans in Magnoliae Flos and a useful tool for the analysis of other complex mixtures. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Microvolume trace environmental analysis using peak-focusing online solid-phase extraction-nano-liquid chromatography-high-resolution mass spectrometry.

PubMed

Stravs, Michael A; Mechelke, Jonas; Ferguson, P Lee; Singer, Heinz; Hollender, Juliane

2016-03-01

Online solid-phase extraction was combined with nano-liquid chromatography coupled to high-resolution mass spectrometry (HRMS) for the analysis of micropollutants in environmental samples from small volumes. The method was validated in surface water, Microcystis aeruginosa cell lysate, and spent Microcystis growth medium. For 41 analytes, quantification limits of 0.1-28 ng/L (surface water) and 0.1-32 ng/L (growth medium) were obtained from only 88 μL of sample. In cell lysate, quantification limits ranged from 0.1-143 ng/L or 0.33-476 ng/g dry weight from a sample of 88 μL, or 26 μg dry weight, respectively. The method matches the sensitivity of established online and offline solid-phase extraction-liquid chromatography-mass spectrometry methods but requires only a fraction of the sample used by those techniques, and is among the first applications of nano-LC-MS for environmental analysis. The method was applied to the determination of bioconcentration in Microcystis aeruginosa in a laboratory experiment, and the benefit of coupling to HRMS was demonstrated in a transformation product screening.

A combined Eulerian-volume of fraction-Lagrangian method for atomization simulation

NASA Technical Reports Server (NTRS)

Seung, S. P.; Chen, C. P.; Ziebarth, John P.

1994-01-01

The tracking of free surfaces between liquid and gas phases and analysis of the interfacial phenomena between the two during the atomization and breakup process of a liquid fuel jet is modeled. Numerical modeling of liquid-jet atomization requires the resolution of different conservation equations. Detailed formulation and validation are presented for the confined dam broken problem, the water surface problem, the single droplet problem, a jet breakup problem, and the liquid column instability problem.

Radioisotope measurements of the liquid-gas flow in the horizontal pipeline using phase method

NASA Astrophysics Data System (ADS)

Hanus, Robert; Zych, Marcin; Jaszczur, Marek; Petryka, Leszek; Świsulski, Dariusz

2018-06-01

The paper presents application of the gamma-absorption method to a two-phase liquid-gas flow investigation in a horizontal pipeline. The water-air mixture was examined by a set of two Am-241 radioactive sources and two NaI(Tl) scintillation probes. For analysis of the electrical signals obtained from detectors the cross-spectral density function (CSDF) was applied. Results of the gas phase average velocity measurements for CSDF were compared with results obtained by application of the classical cross-correlation function (CCF). It was found that the combined uncertainties of the gas-phase velocity in the presented experiments did not exceed 1.6% for CSDF method and 5.5% for CCF.

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.

Chromatic patchy particles: Effects of specific interactions on liquid structure

DOE PAGES

Vasilyev, Oleg A.; Tkachenko, Alexei V.; Klumov, Boris A.

2015-07-13

We study the structural and thermodynamic properties of patchy particle liquids, with a special focus on the role of “color,” i.e., specific interactions between individual patches. A possible experimental realization of such “chromatic” interactions is by decorating the particle patches with single-stranded DNA linkers. The complementarity of the linkers can promote selective bond formation between predetermined pairs of patches. By using MD simulations, we compare the local connectivity, the bond orientation order, and other structural properties of the aggregates formed by the “colored” and “colorless” systems. The analysis is done for spherical particles with two different patch arrangements (tetrahedral andmore » cubic). It is found that the aggregated (liquid) phase of the “colorless” patchy particles is better connected, denser and typically has stronger local order than the corresponding “colored” one. This, in turn, makes the colored liquid less stable thermodynamically. Specifically, we predict that in a typical case the chromatic interactions should increase the relative stability of the crystalline phase with respect to the disordered liquid, thus expanding its region in the phase diagram.« less

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

Lobo, R.; Revah, S.; Viveros-Garcia, T.

An analysis of the local processes occurring in a trickle-bed bioreactor (TBB) with a first-order bioreaction shows that the identification of the TBB operating regime requires knowledge of the substrate concentration in the liquid phase. If the substrate liquid concentration is close to 0, the rate-controlling step is mass transfer at the gas-liquid interface; when it is close to the value in equilibrium with the gas phase, the controlling step is the phenomena occurring in the biofilm, CS{sub 2} removal rate data obtained in a TBB with a Thiobacilii consortia biofilm are analyzed to obtain the mass transfer and kineticmore » parameters, and to show that the bioreactor operates in a regime mainly controlled by mass transfer. A TBB model with two experimentally determined parameters is developed and used to show how the bioreactor size depends on the rate-limiting step, the absorption factor, the substrate fractional conversion, and on the gas and liquid contact pattern. Under certain conditions, the TBB size is independent of the flowing phases` contact pattern. The model effectively describes substrate gas and liquid concentration data for mass transfer and biodegradation rate controlled processes.« less

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.

Successive disorder to disorder phase transitions in ionic liquid [HMIM][BF4] under high pressure

NASA Astrophysics Data System (ADS)

Zhu, Xiang; Yuan, Chaosheng; Li, Haining; Zhu, Pinwen; Su, Lei; Yang, Kun; Wu, Jie; Yang, Guoqiang; Liu, Jing

2016-02-01

In situ high-pressure Raman spectroscopy and synchrotron X-ray diffraction have been employed to investigate the phase behavior of ionic liquid, 1-hexyl-3-methylimidazolium tetrafluoroborate ([HMIM][BF4]) under high pressure up to 20 GPa at room temperature. With increasing pressure, some characteristic bands of [HMIM][BF4] disappear, and some characteristic bands of [HMIM][BF4] display non-monotonic pressure-induced frequency shift and non-monotonic variation of full width at half-maximum. Two successive phase transitions at ˜1.7 GPa and 7.3 GPa have been corroborated by the results above. The glass transition pressure (Pg) of [HMIM][BF4] at ˜7.3 GPa has been obtained by ruby R1 line broadening measurements and analysis of synchrotron X-ray diffraction patterns, and its glass transition mechanism is also analyzed in detail. These facts are suggestive of two successive disorder to disorder phase transitions induced by compression, that is, [HMIM][BF4] serves as a superpressurized glass under the pressure above 7.3 GPa, which is similar to the glassy state at low temperature, and a compression-induced liquid to liquid phase transition in [HMIM][BF4] occurs at ˜1.7 GPa. Besides, the conformational equilibrium of the GAAA conformer and AAAA conformer was converted easily in liquid [HMIM][BF4], while it was difficult to be influenced in glassy state.

Matrix solid-phase dispersion coupled with homogeneous ionic liquid microextraction for the determination of sulfonamides in animal tissues using high-performance liquid chromatography.

PubMed

Wang, Zhibing; He, Mengyu; Jiang, Chunzhu; Zhang, Fengqing; Du, Shanshan; Feng, Wennan; Zhang, Hanqi

2015-12-01

Matrix solid-phase dispersion coupled with homogeneous ionic liquid microextraction was developed and applied to the extraction of some sulfonamides, including sulfamerazine, sulfamethazine, sulfathiazole, sulfachloropyridazine, sulfadoxine, sulfisoxazole, and sulfaphenazole, in animal tissues. High-performance liquid chromatography was applied to the separation and determination of the target analytes. The solid sample was directly treated by matrix solid-phase dispersion and the eluate obtained was treated by homogeneous ionic liquid microextraction. The ionic liquid was used as the extraction solvent in this method, which may result in the improvement of the recoveries of the target analytes. To avoid using organic solvent and reduce environmental pollution, water was used as the elution solvent of matrix solid-phase dispersion. The effects of the experimental parameters on recoveries, including the type and volume of ionic liquid, type of dispersant, ratio of sample to dispersant, pH value of elution solvent, volume of elution solvent, amount of salt in eluate, amount of ion-pairing agent (NH4 PF6 ), and centrifuging time, were evaluated. When the present method was applied to the analysis of animal tissues, the recoveries of the analytes ranged from 85.4 to 118.0%, and the relative standard deviations were lower than 9.30%. The detection limits for the analytes were 4.3-13.4 μg/kg. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The puzzling first-order phase transition in water–glycerol mixtures

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

Popov, Ivan; Greenbaum; Sokolov, Alexei P.

2015-06-05

Over the last decade, discussions on a possible liquid-liquid transition (LLT) have strongly intensified. The LLT proposed by several authors focused mostly on explaining the anomalous properties of water in a deeply supercooled state. However, there have been no direct experimental observations yet of LLT in bulk water in the so-called 'no man's land', where water exists only in the crystalline states. Recently, a novel experimental strategy to detect LLT in water has been employed using water-glycerol (W-G) mixtures, because glycerol can generate a strong hindrance for water crystallization. As a result, the observed first-order phase transition at a concentrationmore » of glycerol around c(g) approximate to 20 mol% was ascribed to the LLT. Here we show unambiguously that the first order phase transition in W-G mixtures is caused by the ice formation. We provide additional dielectric measurements, applying specific annealing temperature protocols in order to reinforce this conclusion. We also provide an explanation, why such a phase transition occurs only in the narrow glycerol concentration range. These results clearly demonstrate the danger of analysis of phase-separating liquids to gain better insights into water dynamics. These liquids have complex phase behavior that is affected by temperature, phase stability and segregation, viscosity and nucleation, and finally by crystallization, that might lead to significant misinterpretations.« less

Robotic solid phase extraction and high performance liquid chromatographic analysis of ranitidine in serum or plasma.

PubMed

Lloyd, T L; Perschy, T B; Gooding, A E; Tomlinson, J J

1992-01-01

A fully automated assay for the analysis of ranitidine in serum and plasma, with and without an internal standard, was validated. It utilizes robotic solid phase extraction with on-line high performance liquid chromatographic (HPLC) analysis. The ruggedness of the assay was demonstrated over a three-year period. A Zymark Py Technology II robotic system was used for serial processing from initial aspiration of samples from original collection containers, to final direct injection onto the on-line HPLC system. Automated serial processing with on-line analysis provided uniform sample history and increased productivity by freeing the chemist to analyse data and perform other tasks. The solid phase extraction efficiency was 94% throughout the assay range of 10-250 ng/mL. The coefficients of variation for within- and between-day quality control samples ranged from 1 to 6% and 1 to 5%, respectively. Mean accuracy for between-day standards and quality control results ranged from 97 to 102% of the respective theoretical concentrations.

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

Ionic liquid and aqueous two-phase extraction based on salting-out coupled with high-performance liquid chromatography for the determination of seven rare ginsenosides in Xue-Sai-Tong injection.

PubMed

Li, Lan-Jie; Jin, Yong-Ri; Wang, Xiao-Zhong; Liu, Ying; Wu, Qian; Shi, Xiao-Lei; Li, Xu-Wen

2015-09-01

A method of ionic liquid salt aqueous two-phase extraction coupled with high-performance liquid chromatography has been developed for the analysis of seven rare ginsenosides including Rg6 , F4 , 20(S)-Rg3 , 20(R)-Rg3 , Rk3 , Rk1 , and Rg5 in Xue-Sai-Tong injection. The injection was mixed with ionic liquid 1-butyl-3-methylimidazolium bromide aqueous solution, and a mixture was obtained. With the addition of sodium dodecyl sulfate and dipotassium phosphate into the mixture, the aqueous two-phase mixture was formed after ultrasonic treatment and centrifuged. Rare ginsenosides were extracted into the upper phase. To obtain a high extraction factors, various influences were considered systematically, such as the volume of ionic liquid, the category and amount of salts, the amount of sodium dodecyl sulfate, the pH value of system, and the time of ultrasonic treatment. Under the optimal condition, rare ginsenosides in Xue-Sai-Tong injection were enriched and detected, the recoveries of seven rare ginsenosides ranged from 90.05 to 112.55%, while relative standard deviations were lower than 2.50%. The developed method was reliable, rapid and sensitive for the determination of seven rare ginsenosides in the injections. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fully automated method for the liquid chromatographic determination of cyproterone acetate in plasma using restricted access material for sample pre-treatment.

PubMed

Christiaens, B; Chiap, P; Rbeida, O; Cello, D; Crommen, J; Hubert, Ph

2003-09-25

A new fully automated method for the quantitative analysis of an antiandrogenic substance, cyproterone acetate (CPA), in plasma samples has been developed using on-line solid-phase extraction (SPE) prior to the determination by reversed-phase liquid chromatography (LC). The automated method was based on the use of a precolumn packed with an internal-surface reversed-phase packing material (LiChrospher RP-4 ADS) for sample clean-up coupled to LC analysis on an octadecyl stationary phase using a column-switching system. A 200-microL volume of plasma sample was injected directly on the precolumn packed with restricted access material using a mixture of water-acetonitrile (90:10, v/v) as washing liquid. The analyte was then eluted in the back-flush mode with the LC mobile phase which consisted of a mixture of phosphate buffer, pH 7.0-acetonitrile (54:46, v/v). The elution profiles of CPA and blank plasma samples on the precolumn and the time needed for analyte transfer from the precolumn to the analytical column were determined. Different compositions of washing liquid and mobile phase were tested to reduce the interference of plasma endogenous components. UV detection was achieved at 280 nm. Finally, the developed method was validated using a new approach, namely the application of the accuracy profile based on the interval confidence at 90% of the total measurement error (bias+standard deviation). The limit of quantification of cyproterone acetate in plasma was determined at 15 ng mL(-1). The validated method should be applicable to the determination of CPA in patients treated by at least 50 mg day(-1).

Advantages of using tetrahydrofuran-water as mobile phases in the quantitation of cyclosporin A in monkey and rat plasma by liquid chromatography-tandem mass spectrometry.

PubMed

Li, Austin C; Li, Yinghe; Guirguis, Micheal S; Caldwell, Robert G; Shou, Wilson Z

2007-01-04

A new analytical method is described here for the quantitation of anti-inflammatory drug cyclosporin A (CyA) in monkey and rat plasma. The method used tetrahydrofuran (THF)-water mobile phases to elute the analyte and internal standard, cyclosporin C (CyC). The gradient mobile phase program successfully eluted CyA into a sharp peak and therefore improved resolution between the analyte and possible interfering materials compared with previously reported analytical approaches, where CyA was eluted as a broad peak due to the rapid conversion between different conformers. The sharp peak resulted from this method facilitated the quantitative calculation as multiple smoothing and large number of bunching factors were not necessary. The chromatography in the new method was performed at 30 degrees C instead of 65-70 degrees C as reported previously. Other advantages of the method included simple and fast sample extraction-protein precipitation, direct injection of the extraction supernatant to column for analysis, and elimination of evaporation and reconstitution steps, which were needed in solid phase extraction or liquid-liquid extraction reported before. This method is amenable to high-throughput analysis with a total chromatographic run time of 3 min. This approach has been verified as sensitive, linear (0.977-4000 ng/mL), accurate and precise for the quantitation of CyA in monkey and rat plasma. However, compared with the usage of conventional mobile phases, the only drawback of this approach was the reduced detection response from the mass spectrometer that was possibly caused by poor desolvation in the ionization source. This is the first report to demonstrate the advantages of using THF-water mobile phases to elute CyA in liquid chromatography.

Phase diagram and universality of the Lennard-Jones gas-liquid system.

PubMed

Watanabe, Hiroshi; Ito, Nobuyasu; Hu, Chin-Kun

2012-05-28

The gas-liquid phase transition of the three-dimensional Lennard-Jones particles system is studied by molecular dynamics simulations. The gas and liquid densities in the coexisting state are determined with high accuracy. The critical point is determined by the block density analysis of the Binder parameter with the aid of the law of rectilinear diameter. From the critical behavior of the gas-liquid coexisting density, the critical exponent of the order parameter is estimated to be β = 0.3285(7). Surface tension is estimated from interface broadening behavior due to capillary waves. From the critical behavior of the surface tension, the critical exponent of the correlation length is estimated to be ν = 0.63(4). The obtained values of β and ν are consistent with those of the Ising universality class.

High-performance liquid chromatographic determination of the beta2-selective adrenergic agonist fenoterol in human plasma after fluorescence derivatization.

PubMed

Kramer, S; Blaschke, G

2001-02-10

A sensitive high-performance liquid chromatographic method has been developed for the determination of the beta2-selective adrenergic agonist fenoterol in human plasma. To improve the sensitivity of the method, fenoterol was derivatized with N-(chloroformyl)-carbazole prior to HPLC analysis yielding highly fluorescent derivatives. The assay involves protein precipitation with acetonitrile, liquid-liquid-extraction of fenoterol from plasma with isobutanol under alkaline conditions followed by derivatization with N-(chloroformyl)-carbazole. Reversed-phase liquid chromatographic determination of the fenoterol derivative was performed using a column-switching system consisting of a LiChrospher 100 RP 18 and a LiChrospher RP-Select B column with acetonitrile, methanol and water as mobile phase. The limit of quantitation in human plasma was 376 pg fenoterol/ml. The method was successfully applied for the assay of fenoterol in patient plasma.

Systematic Assessment of Seven Solvent and Solid-Phase Extraction Methods for Metabolomics Analysis of Human Plasma by LC-MS

NASA Astrophysics Data System (ADS)

Sitnikov, Dmitri G.; Monnin, Cian S.; Vuckovic, Dajana

2016-12-01

The comparison of extraction methods for global metabolomics is usually executed in biofluids only and focuses on metabolite coverage and method repeatability. This limits our detailed understanding of extraction parameters such as recovery and matrix effects and prevents side-by-side comparison of different sample preparation strategies. To address this gap in knowledge, seven solvent-based and solid-phase extraction methods were systematically evaluated using standard analytes spiked into both buffer and human plasma. We compared recovery, coverage, repeatability, matrix effects, selectivity and orthogonality of all methods tested for non-lipid metabolome in combination with reversed-phased and mixed-mode liquid chromatography mass spectrometry analysis (LC-MS). Our results confirmed wide selectivity and excellent precision of solvent precipitations, but revealed their high susceptibility to matrix effects. The use of all seven methods showed high overlap and redundancy which resulted in metabolite coverage increases of 34-80% depending on LC-MS method employed as compared to the best single extraction protocol (methanol/ethanol precipitation) despite 7x increase in MS analysis time and sample consumption. The most orthogonal methods to methanol-based precipitation were ion-exchange solid-phase extraction and liquid-liquid extraction using methyl-tertbutyl ether. Our results help facilitate rational design and selection of sample preparation methods and internal standards for global metabolomics.

Systematic Assessment of Seven Solvent and Solid-Phase Extraction Methods for Metabolomics Analysis of Human Plasma by LC-MS

PubMed Central

Sitnikov, Dmitri G.; Monnin, Cian S.; Vuckovic, Dajana

2016-01-01

The comparison of extraction methods for global metabolomics is usually executed in biofluids only and focuses on metabolite coverage and method repeatability. This limits our detailed understanding of extraction parameters such as recovery and matrix effects and prevents side-by-side comparison of different sample preparation strategies. To address this gap in knowledge, seven solvent-based and solid-phase extraction methods were systematically evaluated using standard analytes spiked into both buffer and human plasma. We compared recovery, coverage, repeatability, matrix effects, selectivity and orthogonality of all methods tested for non-lipid metabolome in combination with reversed-phased and mixed-mode liquid chromatography mass spectrometry analysis (LC-MS). Our results confirmed wide selectivity and excellent precision of solvent precipitations, but revealed their high susceptibility to matrix effects. The use of all seven methods showed high overlap and redundancy which resulted in metabolite coverage increases of 34–80% depending on LC-MS method employed as compared to the best single extraction protocol (methanol/ethanol precipitation) despite 7x increase in MS analysis time and sample consumption. The most orthogonal methods to methanol-based precipitation were ion-exchange solid-phase extraction and liquid-liquid extraction using methyl-tertbutyl ether. Our results help facilitate rational design and selection of sample preparation methods and internal standards for global metabolomics. PMID:28000704

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

PubMed

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

2012-08-14

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

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.

Solid-phase extraction assisted dispersive liquid-liquid microextraction based on solidification of floating organic droplet to determine sildenafil and its analogues in dietary supplements.

PubMed

Li, Jing; Roh, Si Hun; Shaodong, Jia; Hong, Ji Yeon; Lee, Dong-Kyu; Shin, Byong-Kyu; Park, Jeong Hill; Lee, Jeongmi; Kwon, Sung Won

2017-08-01

A novel analytical method for the simultaneous determination of the concentration of sildenafil and its five analogues in dietary supplements using solid-phase extraction assisted reversed-phase dispersive liquid-liquid microextraction based on solidification of floating organic droplet combined with ion-pairing liquid chromatography with an ultraviolet detector was developed. Parameters that affect extraction efficiency were systematically investigated, including the type of solid-phase extraction cartridge, pH of the extraction environment, and the type and volume of extraction and dispersive solvent. The method linearity was in the range of 5.0-100 ng/mL for sildenafil, homosildenafil, udenafil, benzylsildenafil, and thiosildenafil and 10-100 ng/mL for acetildenafil. The coefficients of determination were ≥0.996 for all regression curves. The sensitivity values expressed as limit of detection were between 2.5 and 7.5 ng/mL. Furthermore, intraday and interday precisions expressed as relative standard deviations were less than 5.7 and 9.9%, respectively. The proposed method was successfully applied to the analysis of sildenafil and its five analogues in complex dietary supplements. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Anomalous contact angle hysteresis of a captive bubble: advancing contact line pinning.

PubMed

Hong, Siang-Jie; Chang, Feng-Ming; Chou, Tung-He; Chan, Seong Heng; Sheng, Yu-Jane; Tsao, Heng-Kwong

2011-06-07

Contact angle hysteresis of a sessile drop on a substrate consists of continuous invasion of liquid phase with the advancing angle (θ(a)) and contact line pinning of liquid phase retreat until the receding angle (θ(r)) is reached. Receding pinning is generally attributed to localized defects that are more wettable than the rest of the surface. However, the defect model cannot explain advancing pinning of liquid phase invasion driven by a deflating bubble and continuous retreat of liquid phase driven by the inflating bubble. A simple thermodynamic model based on adhesion hysteresis is proposed to explain anomalous contact angle hysteresis of a captive bubble quantitatively. The adhesion model involves two solid–liquid interfacial tensions (γ(sl) > γ(sl)′). Young’s equation with γ(sl) gives the advancing angle θ(a) while that with γ(sl)′ due to surface rearrangement yields the receding angle θ(r). Our analytical analysis indicates that contact line pinning represents frustration in surface free energy, and the equilibrium shape corresponds to a nondifferential minimum instead of a local minimum. On the basis of our thermodynamic model, Surface Evolver simulations are performed to reproduce both advancing and receding behavior associated with a captive bubble on the acrylic glass.

ANALYSIS OF A GAS-PHASE PARTITIONING TRACER TEST CONDUCTED IN AN UNSATURATED FRACTURED-CLAY FORMATION

EPA Science Inventory

The gas-phase partitioning tracer method was used to estimate non-aqueous phase liquid (NAPL), water, and air saturations in the vadose zone at a chlorinated-solvent contaminated field site in Tucson, AZ. The tracer test was conducted in a fractured-clay system that is the confin...

Characterizing the information content of cloud thermodynamic phase retrievals from the notional PACE OCI shortwave reflectance measurements

NASA Astrophysics Data System (ADS)

Coddington, O. M.; Vukicevic, T.; Schmidt, K. S.; Platnick, S.

2017-08-01

We rigorously quantify the probability of liquid or ice thermodynamic phase using only shortwave spectral channels specific to the National Aeronautics and Space Administration's Moderate Resolution Imaging Spectroradiometer, Visible Infrared Imaging Radiometer Suite, and the notional future Plankton, Aerosol, Cloud, ocean Ecosystem imager. The results show that two shortwave-infrared channels (2135 and 2250 nm) provide more information on cloud thermodynamic phase than either channel alone; in one case, the probability of ice phase retrieval increases from 65 to 82% by combining 2135 and 2250 nm channels. The analysis is performed with a nonlinear statistical estimation approach, the GEneralized Nonlinear Retrieval Analysis (GENRA). The GENRA technique has previously been used to quantify the retrieval of cloud optical properties from passive shortwave observations, for an assumed thermodynamic phase. Here we present the methodology needed to extend the utility of GENRA to a binary thermodynamic phase space (i.e., liquid or ice). We apply formal information content metrics to quantify our results; two of these (mutual and conditional information) have not previously been used in the field of cloud studies.

Effect of titanium addition on the thermal properties of diamond/cu-ti composites fabricated by pressureless liquid-phase sintering technique.

PubMed

Chung, Chih-Yu; Chu, Chao-Hung; Lee, Mu-Tse; Lin, Chun-Ming; Lin, Su-Jien

2014-01-01

In this study, minor-addition elements such as Si, Co, Cr, W, Mo, and Ti were added to matrix to improve the wettability between the diamonds and Cu matrix. The pressureless liquid-phase sintering technique adopted in this study provides a low-cost method for producing diamond/Cu composites with high potential for industrial mass production. Thermal properties of the diamond/Cu-Ti composites fabricated by pressureless liquid-phase sintering at 1373 K with variation in Ti contents were thoroughly investigated. XRD and TEM analysis show that TiC layer formed in the interface between Cu and diamond. The composites exhibited thermal conductivity as high as 620 W/m · K for 50 vol% diamond/Cu-0.6 at % Ti composite with diamond particle size of 300 µm. This value comes up to 85% of the thermal conductivity calculated by the Hasselman and Johnson (H-J) theoretical analysis. Under these conditions, a suitable coefficient of thermal expansion of 6.9 ppm/K was obtained.

Effect of Titanium Addition on the Thermal Properties of Diamond/Cu-Ti Composites Fabricated by Pressureless Liquid-Phase Sintering Technique

PubMed Central

Chung, Chih-Yu; Chu, Chao-Hung; Lee, Mu-Tse; Lin, Chun-Ming; Lin, Su-Jien

2014-01-01

In this study, minor-addition elements such as Si, Co, Cr, W, Mo, and Ti were added to matrix to improve the wettability between the diamonds and Cu matrix. The pressureless liquid-phase sintering technique adopted in this study provides a low-cost method for producing diamond/Cu composites with high potential for industrial mass production. Thermal properties of the diamond/Cu-Ti composites fabricated by pressureless liquid-phase sintering at 1373 K with variation in Ti contents were thoroughly investigated. XRD and TEM analysis show that TiC layer formed in the interface between Cu and diamond. The composites exhibited thermal conductivity as high as 620 W/m·K for 50 vol% diamond/Cu-0.6  at % Ti composite with diamond particle size of 300 µm. This value comes up to 85% of the thermal conductivity calculated by the Hasselman and Johnson (H-J) theoretical analysis. Under these conditions, a suitable coefficient of thermal expansion of 6.9 ppm/K was obtained. PMID:24715816

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.

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.

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

NASA Astrophysics Data System (ADS)

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

2016-12-01

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

Fractionalized Fermi liquids and exotic superconductivity in the Kitaev-Kondo lattice

NASA Astrophysics Data System (ADS)

Seifert, Urban F. P.; Meng, Tobias; Vojta, Matthias

2018-02-01

Fractionalized Fermi liquids (FL*) have been introduced as non-Fermi-liquid metallic phases, characterized by coexisting electron-like charge carriers and local moments which form a fractionalized spin liquid. Here we investigate a Kondo lattice model on the honeycomb lattice with Kitaev interactions among the local moments, a concrete model hosting FL* phases based on Kitaev's Z2 spin liquid. We characterize the FL* phases via perturbation theory, and we employ a Majorana-fermion mean-field theory to map out the full phase diagram. Most remarkably we find nematic triplet superconducting phases which mask the quantum phase transition between fractionalized and conventional Fermi liquid phases. Their pairing structure is inherited from the Kitaev spin liquid; i.e., superconductivity is driven by Majorana glue.

Carboxylate modified porous graphitic carbon: a new class of hydrophilic interaction liquid chromatography phases.

PubMed

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

2013-06-18

Stationary phases for hydrophilic interaction liquid chromatography (HILIC) are predominantly based on silica and polymer supports. We present porous graphitic carbon particles with covalently attached carboxylic acid groups (carboxylate-PGC) as a new HILIC stationary phase. PGC particles were modified by adsorbing the diazonium salt of 4-aminobenzoic acid onto the PGC, followed by reduction of the adsorbed salt with sodium borohydride. The newly developed carboxylate-PGC phase exhibits different selectivity than that of 35 HPLC columns, including bare silica, zwitterionic, amine, reversed, and unmodified PGC phases. Carboxylate-PGC is stable from pH 2.0 to 12.6, yielding reproducible retention even at pH 12.6. Characterization of the new phase is presented by X-ray photoelectron spectroscopy, thermogravimetry, zeta potentials, and elemental analysis. The chromatographic performance of carboxylate-PGC as a HILIC phase is illustrated by separations of carboxylic acids, nucleotides, phenols, and amino acids.

Development of a novel ultrasound-assisted headspace liquid-phase microextraction and its application to the analysis of chlorophenols in real aqueous samples.

PubMed

Xu, Hui; Liao, Ying; Yao, Jinrong

2007-10-05

A new sample pretreatment technique, ultrasound-assisted headspace liquid-phase microextraction was developed as mentioned in this paper. In the technique, the volatile analytes were headspace extracted into a small drop of solvent, which suspended on the bottom of a cone-shaped PCR tube instead of the needle tip of a microsyringe. More solvent could be suspended in the PCR tube than microsyringe due to the larger interfacial tension, thus the analysis sensitivity was significantly improved with the increase of the extractant volume. Moreover, ultrasound-assisted extraction and independent controlling temperature of the extractant and the sample were performed to enhance the extraction efficiency. Following the extraction, the solvent-loaded sample was analyzed by high-performance liquid chromatography. Chlorophenols (2-chlorophenol, 2,4-dichlorophenol and 2,6-dichlorophenol) were chosen as model analytes to investigate the feasibility of the method. The experimental conditions related to the extraction efficiency were systematically studied. Under the optimum experimental conditions, the detection limit (S/N=3), intra- and inter-day RSD were 6 ng mL(-1), 4.6%, 3.9% for 2-chlorophenol, 12 ng mL(-1), 2.4%, 8.8% for 2,4-dichlorophenol and 23 ng mL(-1), 3.3%, 5.3% for 2,6-dichlorophenol, respectively. The proposed method was successfully applied to determine chlorophenols in real aqueous samples. Good recoveries ranging from 84.6% to 100.7% were obtained. In addition, the extraction efficiency of our method and the conventional headspace liquid-phase microextraction were compared; the extraction efficiency of the former was about 21 times higher than that of the latter. The results demonstrated that the proposed method is a promising sample pretreatment approach, its advantages over the conventional headspace liquid-phase microextraction include simple setup, ease of operation, rapidness, sensitivity, precision and no cross-contamination. The method is very suitable for the analysis of trace volatile and semivolatile pollutants in real aqueous sample.

Supercooling effects in faceted eutectic Nb-Si alloys

NASA Technical Reports Server (NTRS)

Gokhale, A. B.; Sarkar, G.; Abbaschian, G. J.; Haygarth, J. C.; Wojcik, C.

1988-01-01

The effect of melt supercooling on the microstructure of an Nb-58 at. pct Si alloy is investigated experimentally using an electromagnetic levitation apparatus. It is found that, starting with an alloy nominally of eutectic composition, nucleation of Nb5Si3 occurs in the supercooled liquid first. Upon further cooling, the remaining liquid continues to supercool until the second phase, NbSi2 is nucleated, which is commonly accompanied by rapid recalescence. The primary phase exibits a eutectoid-type decomposition. The observations are discussed with reference to the results of quantitative microstructural measurements, compositional and thermal analysis, and preliminary thermodynamic modeling of the phase diagram.

Analysis of partial discharge activity by a conducting particle in liquid nitrogen under AC voltages adopting UHF technique

NASA Astrophysics Data System (ADS)

Sarathi, R.; Giridhar, A. V.; Sethupathi, K.

2010-01-01

Liquid nitrogen (LN 2) is used as an insulant as well as coolant in high temperature superconducting power equipments. Particle contamination in liquid nitrogen is one of the major cause for formation of partial discharges during operation. An attempt has been made in the present study to understand the feasibility of using Ultra High Frequency (UHF) sensors for identification of partial discharge (PD) formed due to particle movement in liquid nitrogen under AC voltages. It is observed that the partial discharge formed in LN 2 radiates UHF signal. The results of the study indicate that the conventional partial discharge measurement and UHF peak amplitude measurement have direct correlation. The Phase Resolved Partial Discharge (PRPD) analysis indicates that the partial discharge formed due to particle movement occurs in the entire phase windows of the AC voltage. The PD magnitude increases with increase in applied voltage. The frequency content of UHF signal generated due to particle movement in liquid nitrogen under AC voltages lies in the range of 0.5-1.5 GHz. The UHF sensor output signal analyzed using spectrum analyzer by operating it in zero-span mode, indicates that burst type PD occurs due to particle movement.

Fermionic spin liquid analysis of the paramagnetic state in volborthite

NASA Astrophysics Data System (ADS)

Chern, Li Ern; Schaffer, Robert; Sorn, Sopheak; Kim, Yong Baek

2017-10-01

Recently, thermal Hall effect has been observed in the paramagnetic state of volborthite, which consists of distorted kagome layers with S =1 /2 local moments. Despite the appearance of magnetic order below 1 K , the response to external magnetic field and unusual properties of the paramagnetic state above 1 K suggest possible realization of exotic quantum phases. Motivated by these discoveries, we investigate possible spin liquid phases with fermionic spinon excitations in a nonsymmorphic version of the kagome lattice, which belongs to the two-dimensional crystallographic group p 2 g g . This nonsymmorphic structure is consistent with the spin model obtained in the density functional theory calculation. Using projective symmetry group analysis and fermionic parton mean field theory, we identify twelve distinct Z2 spin liquid states, four of which are found to have correspondence in the eight Schwinger boson spin liquid states we classified earlier. We focus on the four fermionic states with bosonic counterpart and find that the spectrum of their corresponding root U (1 ) states features spinon Fermi surface. The existence of spinon Fermi surface in candidate spin liquid states may offer a possible explanation of the finite thermal Hall conductivity observed in volborthite.

Non-Thermal Plasma in Contact with Water: The Origin of Species.

PubMed

Gorbanev, Yury; O'Connell, Deborah; Chechik, Victor

2016-03-01

Non-thermal atmospheric pressure plasma has attracted considerable attention in recent years due to its potential for biomedical applications. Determining the mechanism of the formation of reactive species in liquid treated with plasma is thus of paramount importance for both fundamental and applied research. In this work, the origin of reactive species in plasma-treated aqueous solutions was investigated by using spin-trapping, hydrogen and oxygen isotopic labelling and electron paramagnetic resonance (EPR) spectroscopy. The species originating from molecules in the liquid phase and those introduced with the feed gas were differentiated by EPR and 1 H NMR analysis of liquid samples. The effects of water vapour and oxygen admixtures in the feed gas were investigated. All the reactive species detected in the liquid samples were shown to be formed largely in the plasma gas phase. It is suggested that hydrogen peroxide (determined by UV/Vis analysis) is formed primarily in the plasma tube, whereas the radical species ⋅OOH, ⋅OH and ⋅H are proposed to originate from the region between the plasma nozzle and the liquid sample. © 2016 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

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.

Mechanical and electro-optical properties of unconventional liquid crystal systems

NASA Astrophysics Data System (ADS)

Liao, Guangxun

Four types of unconventional liquid crystal systems - amphotropic glycolipids; novel bent-core liquid crystals, bent-core liquid crystal and glycolipid mixtures, and colloidal crystal-liquid crystal systems - were studied and characterized by polarizing microscopy, electrical current, digital scanning calorimetry, and dielectric spectroscopy. Thermotropic properties of glycolipids show a number of unusual properties, most notably high (60-120) relative dielectric constants mainly proportional to the number of polar sugar heads. The relaxation of this dielectric mode is found to be governed by the hydrogen bonding between sugar heads. Studies on novel bent-core liquid crystals reveal a new optically isotropic ferroelectric phase, molecular chirality-induced polarity, and transitions between molecular chirality and polarity driven phases. Mixtures of several bent-core substances with nematic, polar SmA and SmC phases, and a simple amphiphilic sugar lipid with SmA mesophase found to obey the well known miscibility rules, i.e. the sugar lipid mixes best with the polar SmA bent-core material. In addition, the chiral sugar lipid was found to induce tilt to the non-tilted polar SmA phase, which represents a new direction among the chirality--polarity--tilt relations. The effects of the surface properties and electric fields were studied on various colloid particles--and liquid crystal systems. It is found that the surface properties (hydrophobicity, roughness, rubbing) of the substrates are important in determining the size and symmetry of colloidal crystals. The director field of the liquid crystal infiltrated in the colloid crystals can be rendered both random and uniform along one of the crystallographic axis. We present the first observations of DC electric-field-induced rotational and translational motion of finite particles in liquid crystals. The electrorotation is essentially identical to the well - known Quincke rotation, which in liquid crystals triggers an additional translational motion at higher fields. Analysis of the electro-rotation and translations provides new ways to probe local rheological properties of liquid crystals.

Method for digital measurement of phase-frequency characteristics for a fixed-length ultrasonic spectrometer

NASA Astrophysics Data System (ADS)

Astashev, M. E.; Belosludtsev, K. N.; Kharakoz, D. P.

2014-05-01

One of the most accurate methods for measuring the compressibility of liquids is resonance measurement of sound velocity in a fixed-length interferometer. This method combines high sensitivity, accuracy, and small sample volume of the test liquid. The measuring principle is to study the resonance properties of a composite resonator that contains a test liquid sample. Ealier, the phase-locked loop (PLL) scheme was used for this. In this paper, we propose an alternative measurement scheme based on digital analysis of harmonic signals, describe the implementation of this scheme using commercially available data acquisition modules, and give examples of test measurements with accuracy evaluations of the results.

Soft-Matter Resistive Sensor for Measuring Shear and Pressure Stresses

NASA Astrophysics Data System (ADS)

Tepayotl-Ramirez, Daniel; Roberts, Peter; Majidi, Carmel

2013-03-01

Building on emerging paradigms in soft-matter electronics, we introduce liquid-phase electronic sensors that simultaneously measures elastic pressure and shear deformation. The sensors are com- posed of a sheet of elastomer that is embedded with fluidic channels containing eutectic Gallium- Indium (EGaIn), a metal alloy that is liquid at room temperature. Applying pressure or shear traction to the surface of the surrounding elastomer causes the elastomer to elastically deform and changes the geometry and electrical properties of the embedded liquid-phase circuit elements. We introduce analytic models that predict the electrical response of the sensor to prescribed surface tractions. These models are validated with both Finite Element Analysis (FEA) and experimental measurements.

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.

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.

Phase change based cooling for high burst mode heat loads with temperature regulation above the phase change temperature

DOEpatents

The United States of America as represented by the United States Department of Energy

2009-12-15

An apparatus and method for transferring thermal energy from a heat load is disclosed. In particular, use of a phase change material and specific flow designs enables cooling with temperature regulation well above the fusion temperature of the phase change material for medium and high heat loads from devices operated intermittently (in burst mode). Exemplary heat loads include burst mode lasers and laser diodes, flight avionics, and high power space instruments. Thermal energy is transferred from the heat load to liquid phase change material from a phase change material reservoir. The liquid phase change material is split into two flows. Thermal energy is transferred from the first flow via a phase change material heat sink. The second flow bypasses the phase change material heat sink and joins with liquid phase change material exiting from the phase change material heat sink. The combined liquid phase change material is returned to the liquid phase change material reservoir. The ratio of bypass flow to flow into the phase change material heat sink can be varied to adjust the temperature of the liquid phase change material returned to the liquid phase change material reservoir. Varying the flowrate and temperature of the liquid phase change material presented to the heat load determines the magnitude of thermal energy transferred from the heat load.

Distortion of liquid film discharging from twin-fluid atomizer

NASA Astrophysics Data System (ADS)

Mehring, C.; Sirignano, W. A.

2001-11-01

The nonlinear distortion and disintegration of a thin liquid film exiting from a two-dimensional twin-fluid atomizer is analyzed numerically. Pulsed gas jets impacting on both sides of the discharging liquid film at the atomizer exit generate dilational and/or sinuous deformations of the film. Both liquid phase and gas phase are inviscid and incompressible. For the liquid phase the so-called long-wavelength approximation is employed yielding a system of unsteady one-dimensional equations for the planar film. Solution of Laplace's equation for the velocity potential yields the gas-phase velocity field on both sides of the liquid stream. Coupling between both phases is described through kinematic and dynamic boundary conditions at the phase interfaces, and includes the solution of the unsteady Bernoulli equation to determine the gas-phase pressure along the interfaces. Both gas- and liquid-phase equations are solved simultaneously. Solution of Laplace's equation for the gas streams is obtained by means of a boundary-element method. Numerical solutions for the liquid phase use the Lax-Wendroff method with Richtmyer splitting. Sheet distortion resulting from the stagnation pressure of the impacting gas jets and subsequent disturbance amplification due to Kelvin-Helmholtz effects are studied for various combinations of gas-pulse timing, gas-jet impact angles, gas-to-liquid-density ratio, liquid-phase Weber number and gas-jet-to-liquid-jet-momentum ratio. Dilational and sinuous oscillations of the liquid are examined and film pinch-off is predicted.

Analysis of quaternary ammonium and phosphonium ionic liquids by reversed-phase high-performance liquid chromatography with charged aerosol detection and unified calibration.

PubMed

Stojanovic, Anja; Lämmerhofer, Michael; Kogelnig, Daniel; Schiesel, Simone; Sturm, Martin; Galanski, Markus; Krachler, Regina; Keppler, Bernhard K; Lindner, Wolfgang

2008-10-31

Several hydrophobic ionic liquids (ILs) based on long-chain aliphatic ammonium- and phosphonium cations and selected aromatic anions were analyzed by reversed-phase high-performance liquid chromatography (RP-HPLC) employing trifluoroacetic acid as ion-pairing additive to the acetonitrile-containing mobile phase and adopting a step-gradient elution mode. The coupling of charged aerosol detection (CAD) for the non-chromophoric aliphatic cations with diode array detection (DAD) for the aromatic anions allowed their simultaneous analysis in a set of new ILs derived from either tricaprylmethylammonium chloride (Aliquat 336) and trihexyltetradecylphosphonium chloride as precursors. Aliquat 336 is a mix of ammonium cations with distinct aliphatic chain lengths. In the course of the studies it turned out that CAD generates an identical detection response for all the distinct aliphatic cations. Due to lack of single component standards of the individual Aliquat 336 cation species, a unified calibration function was established for the quantitative analysis of the quaternary ammonium cations of the ILs. The developed method was validated according to ICH guidelines, which confirmed the validity of the unified calibration. The application of the method revealed molar ratios of cation to anion close to 1 indicating a quantitative exchange of the chloride ions of the precursors by the various aromatic anions in the course of the synthesis of new ILs. Anomalies of CAD observed for the detection of some aromatic anions (thiosalicylate and benzoate) are discussed.

Liquid crystal point diffraction interferometer. Ph.D. Thesis - Arizona Univ., 1995

NASA Technical Reports Server (NTRS)

Mercer, Carolyn R.

1995-01-01

A new instrument, the liquid crystal point diffraction-interferometer (LCPDI), has been developed for the measurement of phase objects. This instrument maintains the compact, robust design of Linnik's point diffraction interferometer (PDI) and adds to it phase stepping capability for quantitative interferogram analysis. The result is a compact, simple to align, environmentally insensitive interferometer capable of accurately measuring optical wavefronts with very high data density and with automated data reduction. This dissertation describes the theory of both the PDI and liquid crystal phase control. The design considerations for the LCPDI are presented, including manufacturing considerations. The operation and performance of the LCPDI are discussed, including sections regarding alignment, calibration, and amplitude modulation effects. The LCPDI is then demonstrated using two phase objects: defocus difference wavefront, and a temperature distribution across a heated chamber filled with silicone oil. The measured results are compared to theoretical or independently measured results and show excellent agreement. A computer simulation of the LCPDI was performed to verify the source of observed periodic phase measurement error. The error stems from intensity variations caused by dye molecules rotating within the liquid crystal layer. Methods are discussed for reducing this error. Algorithms are presented which reduce this error; they are also useful for any phase-stepping interferometer that has unwanted intensity fluctuations, such as those caused by unregulated lasers.

Liquid crystal 'blue phases' with a wide temperature range.

PubMed

Coles, Harry J; Pivnenko, Mikhail N

2005-08-18

Liquid crystal 'blue phases' are highly fluid self-assembled three-dimensional cubic defect structures that exist over narrow temperature ranges in highly chiral liquid crystals. The characteristic period of these defects is of the order of the wavelength of visible light, and they give rise to vivid specular reflections that are controllable with external fields. Blue phases may be considered as examples of tuneable photonic crystals with many potential applications. The disadvantage of these materials, as predicted theoretically and proved experimentally, is that they have limited thermal stability: they exist over a small temperature range (0.5-2 degrees C) between isotropic and chiral nematic (N*) thermotropic phases, which limits their practical applicability. Here we report a generic family of liquid crystals that demonstrate an unusually broad body-centred cubic phase (BP I*) from 60 degrees C down to 16 degrees C. We prove this with optical texture analysis, selective reflection spectroscopy, Kössel diagrams and differential scanning calorimetry, and show, using a simple polarizer-free electro-optic cell, that the reflected colour is switched reversibly in applied electric fields over a wide colour range in typically 10 ms. We propose that the unusual behaviour of these blue phase materials is due to their dimeric molecular structure and their very high flexoelectric coefficients. This in turn sets out new theoretical challenges and potentially opens up new photonic applications.

Effect of Liquid-Crystalline Epoxy Backbone Structure on Thermal Conductivity of Epoxy-Alumina Composites

NASA Astrophysics Data System (ADS)

Giang, Thanhkieu; Kim, Jinhwan

2017-01-01

In a series of papers published recently, we clearly demonstrated that the most important factor governing the thermal conductivity of epoxy-Al2O3 composites is the backbone structure of the epoxy. In this study, three more epoxies based on diglycidyl ester-terminated liquid-crystalline epoxy (LCE) have been synthesized to draw conclusions regarding the effect of the epoxy backbone structure on the thermal conductivity of epoxy-alumina composites. The synthesized structures were characterized by proton nuclear magnetic resonance (1H-NMR) and Fourier-transform infrared (FT-IR) spectroscopy. Differential scanning calorimetry, thermogravimetric analysis, and optical microscopy were also employed to examine the thermal and optical properties of the synthesized LCEs and the cured composites. All three LCE resins exhibited typical liquid-crystalline behaviors: clear solid crystalline state below the melting temperature ( T m), sharp crystalline melting at T m, and transition to nematic phase above T m with consequent isotropic phase above the isotropic temperature ( T i). The LCE resins displayed distinct nematic liquid-crystalline phase over a wide temperature range and retained liquid-crystalline phase after curing, with high thermal conductivity of the resulting composite. The thermal conductivity values ranged from 3.09 W/m-K to 3.89 W/m-K for LCE-Al2O3 composites with 50 vol.% filler loading. The steric effect played a governing role in the difference. The neat epoxy resin thermal conductivity was obtained as 0.35 W/m-K to 0.49 W/m-K based on analysis using the Agari-Uno model. The results clearly support the objective of this study in that the thermal conductivity of the LCE-containing networks strongly depended on the epoxy backbone structure and the degree of ordering in the cured network.

Hydration of dimethyldodecylamine-N-oxide: enthalpy and entropy driven processes.

PubMed

Kocherbitov, Vitaly; Söderman, Olle

2006-07-13

Dimethyldodecylamine-N-oxide (DDAO) has only one polar atom that is able to interact with water. Still, this surfactant shows very hydrophilic properties: in mixtures with water, it forms normal liquid crystalline phases and micelles. Moreover, there is data in the literature indicating that the hydration of this surfactant is driven by enthalpy while other studies show that hydration of surfactants and lipids typically is driven by entropy. Sorption calorimetry allows resolving enthalpic and entropic contributions to the free energy of hydration at constant temperature and thus directly determines the driving forces of hydration. The results of the present sorption calorimetric study show that the hydration of liquid crystalline phases of DDAO is driven by entropy, except for the hydration of the liquid crystalline lamellar phase which is co-driven by enthalpy. The exothermic heat effect of the hydration of the lamellar phase arises from formation of strong hydrogen bonds between DDAO and water. Another issue is the driving forces of the phase transitions caused by the hydration. The sorption calorimetric results show that the transitions from the lamellar to cubic and from the cubic to the hexagonal phase are driven by enthalpy. Transitions from solid phases to the liquid crystalline lamellar phase are entropically driven, while the formation of the monohydrate from the dry surfactant is driven by enthalpy. The driving forces of the transition from the hexagonal phase to the isotropic solution are close to zero. These sorption calorimetric results are in good agreement with the analysis of the binary phase diagram based on the van der Waals differential equation. The phase diagram of the DDAO-water system determined using DSC and sorption calorimetry is presented.

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.

Rapid Quantitative Analysis of Naringenin in the Fruit Bodies of Inonotus vaninii by Two-phase Acid Hydrolysis Followed by Reversed Phase-high Performance Liquid Chromatography-ultra Violet.

PubMed

Guohua, Xia; Pan, Ruirong; Bao, Rui; Ge, Yanru; Zhou, Cunshan; Shen, Yuping

2017-01-01

Sanghuang is one of mystical traditional Chinese medicines recorded earliest 2000 years ago, that included various fungi of Inonotus genus and was well-known for antitumor effect in modern medicine. Inonotus vaninii is grown in natural forest of Northeastern China merely and used as Sanghuang commercially, but it has no quality control specification until now. This study was to establish a rapid method of two-phase acid hydrolysis followed by reversed phase-high performance liquid chromatography-ultra violet (RP-HPLC-UV) to quantify naringenin in the fruit body of I. vaninii . Sample solution was prepared by pretreatment of raw material in two-phase acid hydrolysis and the hydrolysis technology was optimized. After reconstitution, analysis was performed using RP-HPLC-UV. The method validation was investigated and the naringenin content of sample and comparison were determined. The naringenin was obtained by two-phase acid hydrolysis method, namely, 10.0 g of raw material was hydrolyzed in 200 mL of 1% sulfuric acid aqueous solution (v/v) and 400 mL of chloroform in oil bath at 110°C for 2 h. Good linearity ( r = 0.9992) was achieved between concentration of analyte and peak area. The relative standard deviation (RSD) of precision was 2.47% and the RSD of naringenin contents for repeatability was 3.13%. The accuracy was supported with recoveries at 96.37%, 97.30%, and 99.31%. The sample solution prepared using the proposed method contained higher content of naringenin than conventional method and was stable for 8 h. Due to the high efficiency of sample preparation and high reliability of the HPLC method, it is feasible to use this method for routine analysis of naringenin in the fungus. A convenient two-phase acid hydrolysis was employed to produce naringenin from raw material, and then an efficient and reliable reversed phase-high performance liquid chromatography-ultra violet method was established to monitor naringenin in the fruit bodies of Inonotus vaninii . The newly established method could be used to control the quality of the herb. Abbreviations used: RP-HPLC-UV: Reversed Phase-High Performance Liquid Chromatography-Ultra Violet, RSD: Relative Standard Deviation, EtOAc: Ethyl acetate, ACN: Acetonitrile, MeOH: Methanol, RH: Relative Humility.

Spectrophotometric and HPLC Methods for Simultaneous Estimation of Amlodipine Besilate, Losartan Potassium and Hydrochlorothiazide in Tablets

PubMed Central

Wankhede, S. B.; Raka, K. C.; Wadkar, S. B.; Chitlange, S. S.

2010-01-01

Two UV-spectrophotometric and one reverse phase high performance liquid chromatography methods have been developed for the simultaneous estimation of amlodipine besilate, losartan potassium and hydrochlorothiazide in tablet dosage form. The first UV spectrophotometric method was a determination using the simultaneous equation method at 236.5, 254 and 271 nm over the concentration range 5-25, 10-50 and 5-25 μg/ml for amlodipine besilate, losartan potassium and hydrochlorothiazide, respectively. The second UV method was a determination using the area under curve method at 231.5-241.5, 249-259 and 266-276 nm over the concentration range of 5-25, 5-25 and 10-50 μg/ml for amlodipine besilate, hydrochlorothiazide and losartan potassium, respectively. In reverse phase high performance liquid chromatography analysis is carried out using 0.025 M phosphate buffer (pH 3.7):acetonitrile (57:43 v/v) as the mobile phase and Kromasil C18 (4.6 mm i.d×250 mm) column as stationery phase with detection wavelength of 232 nm linearity was obtained in the concentration range of 2-14, 20-140 and 5-40 μg/ml for amlodipine besilate, losartan potassium and hydrochlorothiazide, respectively. Both UV-spectrophotometric and reverse phase high performance liquid chromatography methods were statistically validated and can be used for analysis of combined dose tablet formulation containing amlodipine besilate, losartan potassium and hydrochlorothiazide. PMID:20582208

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.

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.

Quick, easy, cheap, effective, rugged, and safe sample preparation approach for pesticide residue analysis using traditional detectors in chromatography: A review.

PubMed

Rahman, Md Musfiqur; Abd El-Aty, A M; Kim, Sung-Woo; Shin, Sung Chul; Shin, Ho-Chul; Shim, Jae-Han

2017-01-01

In pesticide residue analysis, relatively low-sensitivity traditional detectors, such as UV, diode array, electron-capture, flame photometric, and nitrogen-phosphorus detectors, have been used following classical sample preparation (liquid-liquid extraction and open glass column cleanup); however, the extraction method is laborious, time-consuming, and requires large volumes of toxic organic solvents. A quick, easy, cheap, effective, rugged, and safe method was introduced in 2003 and coupled with selective and sensitive mass detectors to overcome the aforementioned drawbacks. Compared to traditional detectors, mass spectrometers are still far more expensive and not available in most modestly equipped laboratories, owing to maintenance and cost-related issues. Even available, traditional detectors are still being used for analysis of residues in agricultural commodities. It is widely known that the quick, easy, cheap, effective, rugged, and safe method is incompatible with conventional detectors owing to matrix complexity and low sensitivity. Therefore, modifications using column/cartridge-based solid-phase extraction instead of dispersive solid-phase extraction for cleanup have been applied in most cases to compensate and enable the adaptation of the extraction method to conventional detectors. In gas chromatography, the matrix enhancement effect of some analytes has been observed, which lowers the limit of detection and, therefore, enables gas chromatography to be compatible with the quick, easy, cheap, effective, rugged, and safe extraction method. For liquid chromatography with a UV detector, a combination of column/cartridge-based solid-phase extraction and dispersive solid-phase extraction was found to reduce the matrix interference and increase the sensitivity. A suitable double-layer column/cartridge-based solid-phase extraction might be the perfect solution, instead of a time-consuming combination of column/cartridge-based solid-phase extraction and dispersive solid-phase extraction. Therefore, replacing dispersive solid-phase extraction with column/cartridge-based solid-phase extraction in the cleanup step can make the quick, easy, cheap, effective, rugged, and safe extraction method compatible with traditional detectors for more sensitive, effective, and green analysis. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Development and validation of a rapid reverse-phase HPLC method for the determination of methotrexate from nanostructured liquid crystalline systems.

PubMed

Zuben, E S Von; Oliveira, A G; Chorilli, M; Scarpa, M V

2018-03-05

A reversed-phase liquid chromatography (RP-LC) method was successfully developed and validated for the determination of methotrexate in nanostructured liquid crystalline systems composed by polyether functional siloxane and silicone polyether copolymer. The LC method was performed on RP C18-ODS column, Agilent Zorbax® (4.6 x 250 mm, 5 μm), maintained at room temperature, with a mobile phase constituted by a mixture of 50 mM ammonium acetate buffer (pH 6.0) and methanol (77:23,v/v) with a flow rate of 1.0 mL/min, using ultraviolet detection at 313 nm. The parameters used in the validation process were linearity, specificity, intra and inter-day precision, accuracy, robustness. The quantitation and detection limits yielded good results. The calibration plot assumed linear behavior from 5.0-150.0 μg. mL-1 (r2 = 0.9999). The methotrexate was subjected to oxidation, acid, base and neutral degradation, photolysis and heat as stress conditions. There were no interfering peaks at or near the retention time of methotrexate. The nanostructured liquid crystalline systems did not interfere with the analysis and the recovery was quantitative. The intra and inter-day assay relative standard deviation were less than 0.20 %. The method developed proved to be simple, sensitive, accurate, precise, reproducible and therefore adequate for routine analysis of methotrexate in nanostructured liquid crystalline systems.

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.

Indirect measurement of the solid/liquid interface using the minimization technique

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

Choi, H.; Chun, M.

1985-11-01

The phenomenon of solidification of a flowing fluid in a vertical tube is closely related to the relocation dynamics of molten nuclear fuels in hypothetical core-disruptive accidents of a liquid-metal fast breeder reactor. The knowledge of the transient shape and the position of the liquid/solid interface is of practical importance in analysis of phase change processes. Sparrow and Broadbent directly measured the solid liquid interface via experiments, whereas Viskanta observed the solid/liquid interface motion via a photographic method. In this paper, a new method to predict the transient position of the solid/liquid interface is developed. This method is based onmore » the minimization technique. To use this method one needs the temperature of the wall on which the phase change is to take place. The new technique is useful, in particular, for the case of inward solidification of a flowing fluid in a tube where direct measurement of the solid/liquid interface is not possible, whereas the tube wall temperature measurement is relatively easy.« less

Determining phase diagrams of gas-liquid systems using a microfluidic PVT.

PubMed

Mostowfi, Farshid; Molla, Shahnawaz; Tabeling, Patrick

2012-11-07

A novel microfluidic device designed for analyzing phase diagrams of gas-liquid systems (PVT or pressure-volume-temperature measurements) is described. The method mimics the phase transition of a reservoir fluid as it travels through the wellbore from the formation to the surface. The device consists of a long serpentine microchannel etched in a silicon substrate. The local pressure inside the channel is measured using membrane-based optical pressure sensors positioned along the channel. Geometrical restrictions are placed along the microchannel in order to nucleate bubbles when nucleation conditions are met, thus preventing the development of a supersaturation state in the channel. We point out that a local equilibrium state between gas and liquid phases is achieved, which implies that equilibrium properties can be directly measured on the chip. We analyze different mixtures of hydrocarbon systems and, consistently with the preceding analysis, obtain excellent agreement between our technique and conventional measurements. From a practical viewpoint (important for the relevance of the technology), we observe that the measurement time of thermodynamic properties of gas-liquid systems is reduced from hours to minutes with the present device without compromising the measurement accuracy.

Liquid-solid surface phase transformation of fluorinated fullerene on monolayer tungsten diselenide

NASA Astrophysics Data System (ADS)

Song, Zhibo; Wang, Qixing; Li, Ming-Yang; Li, Lain-Jong; Zheng, Yu Jie; Wang, Zhuo; Lin, Tingting; Chi, Dongzhi; Ding, Zijing; Huang, Yu Li; Thye Shen Wee, Andrew

2018-04-01

Hybrid van der Waals heterostructures constructed by the integration of organic molecules and two-dimensional (2D) transition metal dichalcogenide (TMD) materials have useful tunable properties for flexible electronic devices. Due to the chemically inert and atomically smooth nature of the TMD surface, well-defined crystalline organic films form atomically sharp interfaces facilitating optimal device performance. Here, the surface phase transformation of the supramolecular packing structure of fluorinated fullerene (C60F48 ) on single-layer tungsten diselenide (WSe2) is revealed by low-temperature scanning tunneling microscopy, from thermally stable liquid to solid phases as the coverage increases. Statistical analysis of the intermolecular interaction potential reveals that the repulsive dipole-dipole interaction induced by interfacial charge transfer and substrate-mediated interactions play important roles in stabilizing the liquid C60F48 phases. Theoretical calculations further suggest that the dipole moment per C60F48 molecule varies with the surface molecule density, and the liquid-solid transformation could be understood from the perspective of the thermodynamic free energy for open systems. This study offers insights into the growth behavior at 2D organic/TMD hybrid heterointerfaces.

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.

Quantitative analysis of matrine in liquid crystalline nanoparticles by HPLC.

PubMed

Peng, Xinsheng; Li, Baohong; Hu, Min; Ling, Yahao; Tian, Yuan; Zhou, Yanxing; Zhou, Yanfang

2014-01-01

A reversed-phase high-performance liquid chromatographic method has been developed to quantitatively determine matrine in liquid crystal nanoparticles. The chromatographic method is carried out using an isocratic system. The mobile phase was composed of methanol-PBS(pH6.8)-triethylamine (50 : 50 : 0.1%) with a flow rate of 1 mL/min with SPD-20A UV/vis detector and the detection wavelength was at 220 nm. The linearity of matrine is in the range of 1.6 to 200.0  μ g/mL. The regression equation is y = 10706x - 2959 (R (2) = 1.0). The average recovery is 101.7%; RSD = 2.22%  (n = 9). This method provides a simple and accurate strategy to determine matrine in liquid crystalline nanoparticle.

High Performance Liquid Chromatographic Analysis of Phytoplankton Pigments Using a C16-Amide Column

EPA Science Inventory

A reverse-phase high performance liquid chromatographic (RP-HPLC) method was developed to analyze in a single run, most polar and non-polar chlorophylls and carotenoids from marine phytoplankton. The method is based on a RP-C16-Amide column and a ternary gradient system consistin...

Dual-phase gas-permeation flow-injection thermometric analysis for the determination of carbon dioxide.

PubMed

Liu, S J; Tubino, M

1998-11-01

A flow-injection configuration based on a dual-phase gas-permeation system from a liquid donor to a gas acceptor stream with a thermistor flow-through detector is proposed for the direct analysis of the gas in the acceptor. This system was applied for the determination of carbon dioxide (in the form of carbonate) using the following chemical reaction: CO(2)(g)+2NH(3)(g)+H(2)O(g)=(NH(4))(2)CO(3)(s), with a linear response from 1x10(-3) to 50x10(-3) mol l(-1) of CO(3)(2-). Carbon dioxide was produced in the liquid donor and permeated into the gaseous acceptor stream of air/water vapor. The detection limit is 1x10(-3) mol l(-1) of carbonate, and a sampling frequency of 60 h(-1) is achieved with a relative standard deviation of 4.1% for replicate injections. The dual-phase gas-permeation flow-injection manifold, along with the membrane and phase separations, as well as the chemical reaction, provides enhanced selectivity when compared with the system employing a liquid acceptor stream, as serious interferents in this system, for instance, acetate and formate, among others, do not interfere in the proposed system.

Simultaneous Determination of Perfluorinated Compounds in Edible Oil by Gel-Permeation Chromatography Combined with Dispersive Solid-Phase Extraction and Liquid Chromatography-Tandem Mass Spectrometry.

PubMed

Yang, Lili; Jin, Fen; Zhang, Peng; Zhang, Yanxin; Wang, Jian; Shao, Hua; Jin, Maojun; Wang, Shanshan; Zheng, Lufei; Wang, Jing

2015-09-30

A simple analytical method was developed for the simultaneous analysis of 18 perfluorinated compounds (PFCs) in edible oil. The target compounds were extracted by acetonitrile, purified by gel permeation chromatography (GPC) and dispersive solid-phase extraction (DSPE) using graphitized carbon black (GCB) and octadecyl (C18), and analyzed by liquid chromatography-electrospray ionization tandem mass spectrometry (LC-ES-MS/MS) in negative ion mode. Recovery studies were performed at three fortification levels. The average recoveries of all target PFCs ranged from 60 to 129%, with an acceptable relative standard deviation (RSD) (1-20%, n = 3). The method detection limits (MDLs) ranged from 0.004 to 0.4 μg/kg, which was significantly improved compared with the existing liquid-liquid extraction and cleanup method. The method was successfully applied for the analysis of all target PFCs in edible oil samples collected from markets in Beijing, China, and the results revealed that C6-C10 perfluorocarboxylic acid (PFCAs) and C7 perfluorosulfonic acid PFSAs were the major PFCs detected in oil samples.

Determination of dissolved-phase pesticides in surface water from the Yakima River basin, Washington, using the Goulden large-sample extractor and gas chromatography/mass spectrometer

USGS Publications Warehouse

Foster, Gregory D.; Gates, Paul M.; Foreman, William T.; McKenzie, Stuart W.; Rinella, Frank A.

1993-01-01

Concentrations of pesticides in the dissolved phase of surface water samples from the Yakima River basin, WA, were determined using preconcentration in the Goulden large-sample extractor (GLSE) and gas chromatography/mass spectrometry (GC/MS) analysis. Sample volumes ranging from 10 to 120 L were processed with the GLSE, and the results from the large-sample analyses were compared to those derived from 1-L continuous liquid-liquid extractions Few of the 40 target pesticides were detected in 1-L samples, whereas large-sample preconcentration in the GLSE provided detectable levels for many of the target pesticides. The number of pesticides detected in GLSE processed samples was usually directly proportional to sample volume, although the measured concentrations of the pesticides were generally lower at the larger sample volumes for the same water source. The GLSE can be used to provide lower detection levels relative to conventional liquid-liquid extraction in GC/MS analysis of pesticides in samples of surface water.

Quantification of amino acids and peptides in an ionic liquid based aqueous two-phase system by LC-MS analysis.

PubMed

Oppermann, Sebastian; Oppermann, Christina; Böhm, Miriam; Kühl, Toni; Imhof, Diana; Kragl, Udo

2018-04-25

Aqueous two-phase systems (ATPS) occur by the mixture of two polymers or a polymer and an inorganic salt in water. It was shown that not only polymers but also ionic liquids in combination with inorganic cosmotrophic salts are able to build ATPS. Suitable for the formation of ionic liquid-based ATPS systems are hydrophilic water miscible ionic liquids. To understand the driving force for amino acid and peptide distribution in IL-ATPS at different pH values, the ionic liquid Ammoeng 110™ and K 2 HPO 4 have been chosen as a test system. To quantify the concentration of amino acids and peptides in the different phases, liquid chromatography and mass spectrometry (LC-MS) technologies were used. Therefore the peptides and amino acids have been processed with EZ:faast™-Kit from Phenomenex for an easy and reliable quantification method even in complex sample matrices. Partitioning is a surface-dependent phenomenon, investigations were focused on surface-related amino acid respectively peptide properties such as charge and hydrophobicity. Only a very low dependence between the amino acids or peptides hydrophobicity and the partition coefficient was found. Nevertheless, the presented results show that electrostatic respectively ionic interactions between the ionic liquid and the amino acids or peptides have a strong impact on their partitioning behavior.

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.

LIQUID-LIQUID EXTRACTION COLUMNS

DOEpatents

Thornton, J.D.

1957-12-31

This patent relates to liquid-liquid extraction columns having a means for pulsing the liquid in the column to give it an oscillatory up and down movement, and consists of a packed column, an inlet pipe for the dispersed liquid phase and an outlet pipe for the continuous liquid phase located in the direct communication with the liquid in the lower part of said column, an inlet pipe for the continuous liquid phase and an outlet pipe for the dispersed liquid phase located in direct communication with the liquid in the upper part of said column, a tube having one end communicating with liquid in the lower part of said column and having its upper end located above the level of said outlet pipe for the dispersed phase, and a piston and cylinder connected to the upper end of said tube for applying a pulsating pneumatic pressure to the surface of the liquid in said tube so that said surface rises and falls in said tube.

Critical behavior of phase interfaces in porous media: Analysis of scaling properties with the use of noncoherent and coherent light

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

Zimnyakov, D. A., E-mail: zimnykov@sgu.ru; Sadovoi, A. V.; Vilenskii, M. A.

2009-02-15

Image sequences of the surface of disordered layers of porous medium (paper) obtained under noncoherent and coherent illumination during capillary rise of a liquid are analyzed. As a result, principles that govern the critical behavior of the interface between liquid and gaseous phases during its pinning are established. By a cumulant analysis of speckle-modulated images of the surface and by the statistical analysis of binarized difference images of the surface under noncoherent illumination, it is shown that the macroscopic dynamics of the interface at the stage of pinning is mainly controlled by the power law dependence of the appearance ratemore » of local instabilities (avalanches) of the interface on the critical parameter, whereas the growth dynamics of the local instabilities is controlled by the diffusion of a liquid in a layer and weakly depends on the critical parameter. A phenomenological model is proposed for the macroscopic dynamics of the phase interface for interpreting experimental data. The values of critical indices are determined that characterize the samples under test within this model. These values are compared with the results of numerical simulation for discrete models of directed percolation corresponding to the Kardar-Parisi-Zhang equation.« less

Generation and characterization of gas bubbles in liquid metals

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

Eckert, S.; Gerbeth, G.; Witke, W.

1996-06-01

There is an ongoing research performed in the RCR on local transport phenomena in turbulent liquid metal (LM) duct flows exposed to external magnetic fields. In this context so-called MHD flow phenomena can be observed, which are unknown in usual hydraulic engineering. The field of interest covers also the influence of magnetic fields on the behaviour of liquid metal - gas mixtures. Profound knowledge on these LMMHD two-phase flow plays an important role in a variety of technological applications, in particular, in the design of Liquid-Metal MHD generators or for several metallurgical processes employing gas-stirred reactors. However, the highly empiricalmore » nature of two-phase flow analysis gives little hope for the prediction of MHD two-phase flows without extensive experimental data. A summary is given about the authors research activities focussing on two directions: (a) Momentum transfer between gas and liquid metal in a bubbly flow regime to investigate the influence of the external magnetic field on the velocity slip ration S (b) Peculiarities of the MHD turbulence to use small gas bubbles as local tracers in order to study the turbulent mass transfer.« less

Methods to control phase inversions and enhance mass transfer in liquid-liquid dispersions

DOEpatents

Tsouris, Constantinos; Dong, Junhang

2002-01-01

The present invention is directed to the effects of applied electric fields on liquid-liquid dispersions. In general, the present invention is directed to the control of phase inversions in liquid-liquid dispersions. Because of polarization and deformation effects, coalescence of aqueous drops is facilitated by the application of electric fields. As a result, with an increase in the applied voltage, the ambivalence region is narrowed and shifted toward higher volume fractions of the dispersed phase. This permits the invention to be used to ensure that the aqueous phase remains continuous, even at a high volume fraction of the organic phase. Additionally, the volume fraction of the organic phase may be increased without causing phase inversion, and may be used to correct a phase inversion which has already occurred. Finally, the invention may be used to enhance mass transfer rates from one phase to another through the use of phase inversions.

Simultaneous determination of the HIV nucleoside analogue reverse transcriptase inhibitors lamivudine, didanosine, stavudine, zidovudine and abacavir in human plasma by reversed phase high performance liquid chromatography.

PubMed

Verweij-van Wissen, C P W G M; Aarnoutse, R E; Burger, D M

2005-02-25

A reversed phase high performance liquid chromatography method was developed for the simultaneous quantitative determination of the nucleoside reverse transcriptase inhibitors (NRTIs) lamivudine, didanosine, stavudine, zidovudine and abacavir in plasma. The method involved solid-phase extraction with Oasis MAX cartridges from plasma, followed by high performance liquid chromatography with a SymmetryShield RP 18 column and ultraviolet detection set at a wavelength of 260 nm. The assay was validated over the concentration range of 0.015-5 mg/l for all five NRTIs. The average accuracies for the assay were 92-102%, inter- and intra-day coefficients of variation (CV) were <2.5% and extraction recoveries were higher than 97%. This method proved to be simple, accurate and precise, and is currently in use in our laboratory for the quantitative analysis of NRTIs in plasma.

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

Water freezing and ice melting

DOE PAGES

Malolepsza, Edyta; Keyes, Tom

2015-10-12

The generalized replica exchange method (gREM) is designed to sample states with coexisting phases and thereby to describe strong first order phase transitions. The isobaric MD version of the gREM is presented and applied to freezing of liquid water, and melting of hexagonal and cubic ice. It is confirmed that coexisting states are well sampled. The statistical temperature as a function of enthalpy, T S(H), is obtained. Hysteresis between freezing and melting is observed and discussed. The entropic analysis of phase transitions is applied and equilibrium transition temperatures, latent heats, and surface tensions are obtained for hexagonal ice↔liquid and cubicmore » ice↔liquid, with excellent agreement with published values. A new method is given to assign water molecules among various symmetry types. As a result, pathways for water freezing, ultimately leading to hexagonal ice, are found to contain intermediate layered structures built from hexagonal and cubic ice.« less

Determination of effective complex refractive index of a turbid liquid with surface plasmon resonance phase detection.

PubMed

Yingying, Zhang; Jiancheng, Lai; Cheng, Yin; Zhenhua, Li

2009-03-01

The dependence of the surface plasmon resonance (SPR) phase difference curve on the complex refractive index of a sample in Kretschmann configuration is discussed comprehensively, based on which a new method is proposed to measure the complex refractive index of turbid liquid. A corresponding experiment setup was constructed to measure the SPR phase difference curve, and the complex refractive index of turbid liquid was determined. By using the setup, the complex refractive indices of Intralipid solutions with concentrations of 5%, 10%, 15%, and 20% are obtained to be 1.3377+0.0005 i, 1.3427+0.0028 i, 1.3476+0.0034 i, and 1.3496+0.0038 i, respectively. Furthermore, the error analysis indicates that the root-mean-square errors of both the real and the imaginary parts of the measured complex refractive index are less than 5x10(-5).

Characterization of two-phase flow regimes in horizontal tubes using 81mKr tracer experiments.

PubMed

Oriol, Jean; Leclerc, Jean Pierre; Berne, Philippe; Gousseau, Georges; Jallut, Christian; Tochon, Patrice; Clement, Patrice

2008-10-01

The diagnosis of heat exchangers on duty with respect to flow mal-distributions needs the development of non-intrusive inlet-outlet experimental techniques in order to perform an online fault diagnosis. Tracer experiments are an example of such techniques. They can be applied to mono-phase heat exchangers but also to multi-phase ones. In this case, the tracer experiments are more difficult to perform. In order to check for the capabilities of tracer experiments to be used for the flow mal-distribution diagnosis in the case of multi-phase heat exchangers, we present here a preliminary study on the simplest possible system: two-phase flows in a horizontal tube. (81m)Kr is used as gas tracer and properly collimated NaI (TI) crystal scintillators as detectors. The specific shape of the tracer response allows two-phase flow regimes to be characterized. Signal analysis allows the estimation of the gas phase real average velocity and consequently of the liquid phase real average velocity as well as of the volumetric void fraction. These results are compared successfully to those obtained with liquid phase tracer experiments previously presented by Oriol et al. 2007. Characterization of the two-phase flow regimes and liquid dispersion in horizontal and vertical tubes using coloured tracer and no intrusive optical detector. Chem. Eng. Sci. 63(1), 24-34, as well as to those given by correlations from literature.

Layered interfaces between immiscible liquids studied by density-functional theory and molecular-dynamics simulations.

PubMed

Geysermans, P; Elyeznasni, N; Russier, V

2005-11-22

We present a study of the structure in the interface between two immiscible liquids by density-functional theory and molecular-dynamics calculations. The liquids are modeled by Lennard-Jones potentials, which achieve immiscibility by suppressing the attractive interaction between unlike particles. The density profiles of the liquids display oscillations only in a limited part of the simple liquid-phase diagram (rho,T). When approaching the liquid-vapor coexistence, a significant depletion appears while the layering behavior of the density profile vanishes. By analogy with the liquid-vapor interface and the analysis of the adsorption this behavior is suggested to be strongly related to the drying transition.

Characterizing fluid dynamics in a bubble column aimed for the determination of reactive mass transfer

NASA Astrophysics Data System (ADS)

Kováts, Péter; Thévenin, Dominique; Zähringer, Katharina

2018-02-01

Bubble column reactors are multiphase reactors that are used in many process engineering applications. In these reactors a gas phase comes into contact with a fluid phase to initiate or support reactions. The transport process from the gas to the liquid phase is often the limiting factor. Characterizing this process is therefore essential for the optimization of multiphase reactors. For a better understanding of the transfer mechanisms and subsequent chemical reactions, a laboratory-scale bubble column reactor was investigated. First, to characterize the flow field in the reactor, two different methods have been applied. The shadowgraphy technique is used for the characterisation of the bubbles (bubble diameter, velocity, shape or position) for various process conditions. This technique is based on particle recognition with backlight illumination, combined with particle tracking velocimetry (PTV). The bubble trajectories in the column can also be obtained in this manner. Secondly, the liquid phase flow has been analysed by particle image velocimetry (PIV). The combination of both methods, delivering relevant information concerning disperse (bubbles) and continuous (liquid) phases, leads to a complete fluid dynamical characterization of the reactor, which is the pre-condition for the analysis of mass transfer between both phases.

Phase transformations in an ascending adiabatic mixed-phase cloud volume

NASA Astrophysics Data System (ADS)

Pinsky, M.; Khain, A.; Korolev, A.

2015-04-01

Regimes of liquid-ice coexistence that may form in an adiabatic parcel ascending at constant velocity at freezing temperatures are investigated. Four zones with different microphysical structures succeeding one another along the vertical direction have been established. On the basis of a novel balance equation, analytical expressions are derived to determine the conditions specific for each of these zones. In particular, the necessary and sufficient conditions for formation of liquid water phase within an ascending parcel containing only ice particles are determined. The results are compared to findings reported in earlier studies. The role of the Wegener-Bergeron-Findeisen mechanism in the phase transformation is analyzed. The dependence of the phase relaxation time on height in the four zones is investigated on the basis of a novel analytical expression. The results obtained in the study can be instrumental for analysis and interpretation of observed mixed-phase clouds.

Non-conventional solvents in liquid phase microextraction and aqueous biphasic systems.

PubMed

An, Jiwoo; Trujillo-Rodríguez, María J; Pino, Verónica; Anderson, Jared L

2017-06-02

The development of rapid, convenient, and high throughput sample preparation approaches such as liquid phase microextraction techniques have been continuously developed over the last decade. More recently, significant attention has been given to the replacement of conventional organic solvents used in liquid phase microextraction techniques in order to reduce toxic waste and to improve selectivity and/or extraction efficiency. With these objectives, non-conventional solvents have been explored in liquid phase microextraction and aqueous biphasic systems. The utilized non-conventional solvents include ionic liquids, magnetic ionic liquids, and deep eutectic solvents. They have been widely used as extraction solvents or additives in various liquid phase microextraction modes including dispersive liquid-liquid microextraction, single-drop microextraction, hollow fiber-liquid phase microextraction, as well as in aqueous biphasic systems. This review provides an overview into the use of non-conventional solvents in these microextraction techniques in the past 5 years (2012-2016). Analytical applications of the techniques are also discussed. Copyright © 2017 Elsevier B.V. All rights reserved.

High-pressure liquid chromatographic analysis of pramoxine hydrochloride in high lipoid aerosol foam dosage form.

PubMed

Weinberger, R; Mann, B; Posluszny, J

1980-04-01

A rapid and quantitative method for the determination of pramoxine hydrochloride by high-pressure liquid chromatography is presented. The drug is extracted as the salt from a preparation with a high lipoid composition by partitioning it to the aqueous phase of an ether-methanol-water-acetic acid system. The extract is chromatographed on an octadecylsilane bonded packing with a methanol-water-acetic acid-methanesulfonic acid mobile phase. The time required for each separation is approximately 6 min. Analytical recoveries of 100.4 +/- 1.5% were obtained.

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

PubMed

Putzel, G Garbès; Schick, M

2008-11-15

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

A new tunable dispersive liquid-liquid micro extraction method developed for the simultaneous preconcentration of lead and cadmium from lakes water: a multivariate study

NASA Astrophysics Data System (ADS)

Bilal, Muhammad; Kazi, Tasneem Gul; Afridi, Hassan Imran; Ali, Jamshed; Baig, Jameel Ahmed; Arain, Mohammad Balal; Khan, Mustafa

2017-08-01

A green tunable dispersive liquid-liquid micro extraction (TDLLME) technique was established for the simultaneous enrichment of lead (Pb) and cadmium (Cd) from different lakes water before analysis by flame atomic absorption spectrometry (FAAS). A solvent known as tunable polarity solvent (TPS), mixture of 1,8-diazabicyclo-[5.4.0]-undec-7-ene (DBU) and 1-decanol, has been employed as extractant in aqueous medium. In first step this mixture can be made polar by slowly bubbling the antisolvent trigger (CO2) through the solution, which makes a monophasic solution. During this step hydrophobic complexes of the metals with 8-hydroxy quinoline (8-HQ) were extracted by TPS. Then the mixture was switched back to hydrophobic one by heating and/or bubbling nitrogen, turning the mixture into two phases again. In second phase the metals were leached out from the complexes entrapped in TPS, by treating with a solution of nitric acid and exposing the mixture to CO2, which switched the mixture into single phase. Then N2 purging and/or heating again turned the mixture into two phases. The acidic aqueous phase containing the metals was introduced to FAAS for analysis, whereas TPS was recycled for next experiment. Different parameters, affecting the efficiency the technique, were optimized by multivariate approach. The method was applied to certified reference material of water and to a real sample spiked with standards of known concentration, to confirm its validity and accuracy. LOD obtained for Pb and Cd were 0.560 and 0.056 μg L- 1 respectively. The developed method was applied successfully to the real water samples of two lakes of Sindh, Pakistan.

Role of Molecular Structure on X-ray Diffraction in Thermotropic Uniaxial and Biaxial Nematic Liquid Crystal Phases

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

Acharya, Bharat R.; Kang, Shin-Woong; Prasad, Veena

2009-08-27

X-ray diffraction is one of the most definitive methods to determine the structure of condensed matter phases, and it has been applied to unequivocally infer the structures of conventional calamitic and lyotropic liquid crystals. With the advent of bent-core and tetrapodic mesogens and the discovery of the biaxial nematic phase in them, the experimental results require more careful interpretation and analysis. Here, we present ab-initio calculations of X-ray diffraction patterns in the isotropic, uniaxial nematic, and biaxial nematic phases of bent-core mesogens. A simple Meier-Saupe-like molecular distribution function is employed to describe both aligned and unaligned mesophases. The distribution functionmore » is decomposed into two, polar and azimuthal, distribution functions to calculate the effect of the evolution of uniaxial and biaxial nematic orientational order. The calculations provide satisfactory semiquantitative interpretations of experimental results. The calculations presented here should provide a pathway to more refined and quantitative analysis of X-ray diffraction data from the biaxial nematic phase.« less

Role of Molecular Structure on X-ray Diffraction in Uniaxial and Biaxial Phases of Thermotropic Liquid Crystals

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

Acharya, Bharat R.; Kang, Shin-Woong; Prasad, Veena

2009-04-29

X-ray diffraction is one of the most definitive methods to determine the structure of condensed matter phases, and it has been applied to unequivocally infer the structures of conventional calamitic and lyotropic liquid crystals. With the advent of bent-core and tetrapodic mesogens and the discovery of the biaxial nematic phase in them, the experimental results require more careful interpretation and analysis. Here, we present ab-initio calculations of X-ray diffraction patterns in the isotropic, uniaxial nematic, and biaxial nematic phases of bent-core mesogens. A simple Meier-Saupe-like molecular distribution function is employed to describe both aligned and unaligned mesophases. The distribution functionmore » is decomposed into two, polar and azimuthal, distribution functions to calculate the effect of the evolution of uniaxial and biaxial nematic orientational order. The calculations provide satisfactory semiquantitative interpretations of experimental results. The calculations presented here should provide a pathway to more refined and quantitative analysis of X-ray diffraction data from the biaxial nematic phase.« less

Phase-field model of vapor-liquid-solid nanowire growth

NASA Astrophysics Data System (ADS)

Wang, Nan; Upmanyu, Moneesh; Karma, Alain

2018-03-01

We present a multiphase-field model to describe quantitatively nanowire growth by the vapor-liquid-solid (VLS) process. The free-energy functional of this model depends on three nonconserved order parameters that distinguish the vapor, liquid, and solid phases and describe the energetic properties of various interfaces, including arbitrary forms of anisotropic γ plots for the solid-vapor and solid-liquid interfaces. The evolution equations for those order parameters describe basic kinetic processes including the rapid (quasi-instantaneous) equilibration of the liquid catalyst to a droplet shape with constant mean curvature, the slow incorporation of growth atoms at the droplet surface, and crystallization within the droplet. The standard constraint that the sum of the phase fields equals unity and the conservation of the number of catalyst atoms, which relates the catalyst volume to the concentration of growth atoms inside the droplet, are handled via separate Lagrange multipliers. An analysis of the model is presented that rigorously maps the phase-field equations to a desired set of sharp-interface equations for the evolution of the phase boundaries under the constraint of force balance at three-phase junctions (triple points) given by the Young-Herring relation that includes torque term related to the anisotropy of the solid-liquid and solid-vapor interface excess free energies. Numerical examples of growth in two dimensions are presented for the simplest case of vanishing crystalline anisotropy and the more realistic case of a solid-liquid γ plot with cusped minima corresponding to two sets of (10 ) and (11 ) facets. The simulations reproduce many of the salient features of nanowire growth observed experimentally, including growth normal to the substrate with tapering of the side walls, transitions between different growth orientations, and crawling growth along the substrate. They also reproduce different observed relationships between the nanowire growth velocity and radius depending on the growth condition. For the basic normal growth mode, the steady-state solid-liquid interface tip shape consists of a main facet intersected by two truncated side facets ending at triple points. The ratio of truncated and main facet lengths are in quantitative agreement with the prediction of sharp-interface theory that is developed here for faceted nanowire growth in two dimensions.

Experimental study of oblique impact between dry spheres and liquid layers

NASA Astrophysics Data System (ADS)

Ma, Jiliang; Liu, Daoyin; Chen, Xiaoping

2013-09-01

Liquid addition is common in industrial fluidization-based processes. A detailed understanding of collision mechanics of particles with liquid layers is helpful to optimize these processes. The normal impact with liquid has been studied extensively; however, the studies on oblique impact with liquid are scarce. In this work, experiments are conducted to trace Al2O3 spheres obliquely impacting on a surface covered by liquid layers, in which the free-fall spheres are disturbed initially by a horizontal gas flow. The oblique impact exhibits different rebound behaviors from normal collision due to the occurrence of strong rotation. The normal and tangential restitution coefficients (en and et) and liquid bridge rupture time (trup) are analyzed. With increase in liquid layer thickness and viscosity, en and et decline, and trup increases. With increase in tangential velocity, et decreases first and then increases, whereas en remains nearly unchanged, and trup decreases constantly. A modified Stokes number is proposed to further explore the relation between restitution coefficients and the impact parameters. Finally, an analysis of energy dissipation shows that the contact deformation and liquid phase are the two main sources of total energy dissipation. Unexpectedly, the dissipative energy caused by the liquid phase is independent of tangential velocity.

Numerical analysis of natural convection in liquid droplets by phase change

NASA Astrophysics Data System (ADS)

Duh, J. C.; Yang, Wen-Jei

1989-09-01

A numerical analysis is performed on thermocapillary buoyancy convection induced by phase change in a liquid droplet. A finite-difference code is developed using an alternating-direction implicit (ADI) scheme. The intercoupling relation between thermocapillary force, buoyancy force, fluid property, heat transfer, and phase change, along with their effects on the induced flow patterns, are disclosed. The flow is classified into three types: thermocapillary, buoyancy, and combined convection. Among the three mechanisms, the combined convection simulates the experimental observations quite well, and the basic mechanism of the observed convection inside evaporating sessile drops is thus identified. It is disclosed that evaporation initiates unstable convection, while condensation always brings about a stable density distribution which eventually damps out all fluid disturbances. Another numerical model is presented to study the effect of boundary recession due to evaporation, and the 'peeling-off' effect (the removal of the surface layer of fluid by evaporation) is shown to be relevant.

Numerical analysis of natural convection in liquid droplets by phase change

NASA Technical Reports Server (NTRS)

Duh, J. C.; Yang, Wen-Jei

1989-01-01

A numerical analysis is performed on thermocapillary buoyancy convection induced by phase change in a liquid droplet. A finite-difference code is developed using an alternating-direction implicit (ADI) scheme. The intercoupling relation between thermocapillary force, buoyancy force, fluid property, heat transfer, and phase change, along with their effects on the induced flow patterns, are disclosed. The flow is classified into three types: thermocapillary, buoyancy, and combined convection. Among the three mechanisms, the combined convection simulates the experimental observations quite well, and the basic mechanism of the observed convection inside evaporating sessile drops is thus identified. It is disclosed that evaporation initiates unstable convection, while condensation always brings about a stable density distribution which eventually damps out all fluid disturbances. Another numerical model is presented to study the effect of boundary recession due to evaporation, and the 'peeling-off' effect (the removal of the surface layer of fluid by evaporation) is shown to be relevant.

Unique orientations and rotational dynamics of a 1-butyl-3-methyl-imidazolium hexafluorophosphate ionic liquid at the gas-liquid interface: the effects of the hydrogen bond and hydrophobic interactions.

PubMed

Yang, Deshuai; Fu, Fangjia; Li, Li; Yang, Zhen; Wan, Zheng; Luo, Yi; Hu, Na; Chen, Xiangshu; Zeng, Guixiang

2018-05-07

Here we report a series of molecular dynamics simulations for the orientations and rotational dynamics of the 1-butyl-3-methyl-imidazoliumhexafluorophosphate ([BMIM][PF 6 ]) ionic liquid (IL) at the gas-liquid interface. Compared to the bulk phase, the [BMIM] + cations at the interface prefer to orientate themselves with their imidazolium rings perpendicular to the gas-IL interface plane and their butyl chains pointing toward the vacuum phase. Such a preferential orientation can be attributed to the combined effect of the hydrophobic interactions and the optimum loss of hydrogen bonds (HBs). More interestingly, our simulation results demonstrate that the butyl chains of cations exhibit a two-stage rotational behavior at the interface, where the butyl chains are always in the vacuum phase at the first stage and the second stage corresponds to the butyl chains migrating from the vacuum phase into the liquid phase. A further detailed analysis reveals that their rotational motions at the first stage are mainly determined by the weakened HB strength at the interface while those at the second stage are dominated by their hydrophobic interactions. Such a unique rotational behavior of the butyl chains is significantly different from those of the anions and the imidazolium rings of cations at the interface due to the lack of existence of hydrophobic interaction in the cases of the latter two. In addition, a new and simple time correlation function (TCF) was constructed here for the first time to quantitatively identify the relevant hydrophobic interaction of alkyl chains. Therefore, our simulation results provide a molecular-level understanding of the effects of HB and hydrophobic interactions on the unique properties of imidazolium-based ILs at the gas-liquid interface.

Effect of Molecular Flexibility on the Nematic-to-Isotropic Phase Transition for Highly Biaxial Molecular Non-Symmetric Liquid Crystal Dimers

PubMed Central

Sebastián, Nerea; López, David Orencio; Diez-Berart, Sergio; de la Fuente, María Rosario; Salud, Josep; Pérez-Jubindo, Miguel Angel; Ros, María Blanca

2011-01-01

In this work, a study of the nematic (N)–isotropic (I) phase transition has been made in a series of odd non-symmetric liquid crystal dimers, the α-(4-cyanobiphenyl-4’-yloxy)-ω-(1-pyrenimine-benzylidene-4’-oxy) alkanes, by means of accurate calorimetric and dielectric measurements. These materials are potential candidates to present the elusive biaxial nematic (NB) phase, as they exhibit both molecular biaxiality and flexibility. According to the theory, the uniaxial nematic (NU)–isotropic (I) phase transition is first-order in nature, whereas the NB–I phase transition is second-order. Thus, a fine analysis of the critical behavior of the N–I phase transition would allow us to determine the presence or not of the biaxial nematic phase and understand how the molecular biaxiality and flexibility of these compounds influences the critical behavior of the N–I phase transition. PMID:28824100

Solid cation exchange phase to remove interfering anthocyanins in the analysis of other bioactive phenols in red wine.

PubMed

da Silva, Letícia Flores; Guerra, Celito Crivellaro; Klein, Diandra; Bergold, Ana Maria

2017-07-15

Bioactive phenols (BPs) are often targets in red wine analysis. However, other compounds interfere in the liquid chromatography methods used for this analysis. Here, purification procedures were tested to eliminate anthocyanin interference during the determination of 19 red-wine BPs. Liquid chromatography, coupled to a diode array detector (HPLC-DAD) and a mass spectrometer (UPLC-MS), was used to compare the direct injection of the samples with solid-phase extractions: reversed-phase (C18) and strong cation-exchange (SCX). The HPLC-DAD method revealed that, out of 13BPs, only six are selectively analyzed with or without C18 treatment, whereas SCX enabled the detection of all BPs. The recovery with SCX was above 86.6% for eight BPs. Moreover, UPLC-MS demonstrated the potential of SCX sample preparation for the determination of 19BPs. The developed procedure may be extended to the analysis of other red wine molecules or to other analytical methods where anthocyanins may interfere. Copyright © 2017 Elsevier Ltd. All rights reserved.

Sample preparation techniques for the determination of trace residues and contaminants in foods.

PubMed

Ridgway, Kathy; Lalljie, Sam P D; Smith, Roger M

2007-06-15

The determination of trace residues and contaminants in complex matrices, such as food, often requires extensive sample extraction and preparation prior to instrumental analysis. Sample preparation is often the bottleneck in analysis and there is a need to minimise the number of steps to reduce both time and sources of error. There is also a move towards more environmentally friendly techniques, which use less solvent and smaller sample sizes. Smaller sample size becomes important when dealing with real life problems, such as consumer complaints and alleged chemical contamination. Optimal sample preparation can reduce analysis time, sources of error, enhance sensitivity and enable unequivocal identification, confirmation and quantification. This review considers all aspects of sample preparation, covering general extraction techniques, such as Soxhlet and pressurised liquid extraction, microextraction techniques such as liquid phase microextraction (LPME) and more selective techniques, such as solid phase extraction (SPE), solid phase microextraction (SPME) and stir bar sorptive extraction (SBSE). The applicability of each technique in food analysis, particularly for the determination of trace organic contaminants in foods is discussed.

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

NASA Astrophysics Data System (ADS)

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

2013-12-01

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

PFOA and PFOS: Analytics

EPA Science Inventory

EPA Method 537 was developed for the analysis of perfluoroalkyl acids (PFAAs) in drinking water to address the occurrence monitoring needs under EPA’s Unregulated Contaminant Monitoring Regulation (UCMR). The method employs solid-phase extraction with analysis by liquid chr...

Ionic Liquid Fuels for Chemical Propulsion

DTIC Science & Technology

2016-10-31

nucleophilicity in the ionic liquid is critical. Both gas -phase and condensed-phase (CPCM-GIL) density functional theory calculations support the...stability trends in dialkylimidazolium ionic liquids and could be used as a higher accuracy method than the gas -phase DFT approach for predicting thermal...stabilities of ionic liquids in general. One important finding from the comparison of the gas -phase basicities relative to the GIL condensed- phase

Modeling of Hydraulic Fracturing on the Basis of the Particle Method

NASA Astrophysics Data System (ADS)

Berezhnoi, D. V.; Gabsalikova, N. F.; Izotov, V. G.; Miheev, V. V.

2018-01-01

A technique of calculating the deformation of the soil environment when it interacts with a liquid on the basis of the particle method a is realized. To describe the behavior of the solid and liquid phases of the soil, a classical two-parameter Lennard-Jones interaction potential and its modified version proposed by the authors were chosen. The model problem of deformation and partial destruction of a soil massif under strong pressure from the liquid pumped into it is solved. Analysis of the results shows that the use of the modified Lennard-Jones potential for describing the solid phase of the soil environment makes it possible to describe the process of formation of cracks in the soil during hydraulic fracturing of the formation.

Ionic liquids for metal extraction from chalcopyrite: solid, liquid and gas phase studies.

PubMed

Kuzmina, O; Symianakis, E; Godfrey, D; Albrecht, T; Welton, T

2017-08-16

We studied leaching of Cu and Fe from naturally occurring chalcopyrite ore using aqueous solutions of ionic liquids (ILs) based on imidazolium and ethylammonium cations and hydrogensulfate, nitrate, acetate or dicyanamide anions. Liquid, solid and gas phases of the leaching systems were characterised. We have shown that nonoxidative leaching is greatly dependant not only on temperature and pH, but on the anion species of the IL. Solutions of 1-butylimidazolium hydrogen sulfate exhibited the best leaching performance among hydrogen sulphate ILs. We have suggested that the formation of an oxide layer in some ILs may be responsible for a reduced leaching ability. The analysis of the gas phase showed the production of CO 2 and CS 2 in all leached samples. Our results suggested that the CS 2 produced upon leaching could be responsible for decreasing the sulfur, but not oxide, layer on the surface of chalcopyrite samples and therefore more efficient leaching. This is the first study, to our knowledge, to provide a systematic comparison of the leaching performance of ILs composed of different anions and cations and without added oxidants.

Development of Hollow-Fiber Liquid-Phase Microextraction Method for Determination of Urinary trans,trans-Muconic Acid as a Biomarker of Benzene Exposure

PubMed Central

Ghamari, Farhad; Bahrami, Abdulrahman; Yamini, Yadollah; Shahna, Farshid Ghorbani; Moghimbeigi, Abbas

2016-01-01

For the first time, hollow-fiber liquid-phase microextraction combined with high-performance liquid chromatography–ultraviolet was used to extract trans,trans-muconic acid, in urine samples of workers who had been exposed to benzene. The parameters affecting the metabolite extraction were optimized as follows: the volume of sample solution was 11 mL with pH 2, liquid membrane containing dihexyl ether as the supporter, 15% (w/v) of trioctylphosphine oxide as the carrier, the time of extraction was 120 minutes, and stirring rate was 500 rpm. Organic phase impregnated in the pores of a hollow fiber was extracted into 24 µL solution of 0.05 mol L−1 Na2CO3 located inside the lumen of the fiber. Under optimized conditions, a high enrichment factor of 153–182 folds, relative recovery of 83%–92%, and detection limit of 0.001 µg mL−1 were obtained. The method was successfully applied to the analysis of ttMA in real urine samples. PMID:27660405

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.

Liquid Chromatographic Analysis of α-Dicarbonyls Using Girard-T Reagent Derivatives.

PubMed

Lawrence, Glen D; Rahmat, Rozaiha; Makahleh, Ahmad; Saad, Bahruddin

2017-11-01

The measurement of α-dicarbonyls and other degradation products of sugars has become important in view of their toxicity. Although there are several methods used for their analysis, most require long reaction times to form UV absorbing or fluorescent derivatives and the nonpolar nature of commonly used derivatives necessitates relatively high concentrations of organic solvents for elution in reverse phase liquid chromatography. The present method describes the use of Girard-T reagent in a simple, one step derivatization of α-dicarbonyls and conjugated aldehydes and analysis using ion-pair reverse phase liquid chromatography. The limit of detection was in the range of 0.06-0.09 μM (4-12 ng/mL) for glyoxal, methylglyoxal, 3-deoxyglucosone and 5-hydroxymethylfurfural with good linear response and reproducibility using UV detection. The hydrazone derivatives were stable for several days in solution. The method was used to study degradation of several sugars and quantification of the target α-dicarbonyls and 5-hydroxymethylfurfural in several soft drinks. © The Author 2017. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

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

Electric-field triggered controlled release of bioactive volatiles from imine-based liquid crystalline phases.

PubMed

Herrmann, Andreas; Giuseppone, Nicolas; Lehn, Jean-Marie

2009-01-01

Application of an electric field to liquid crystalline film forming imines with negative dielectric anisotropy, such as N-(4-methoxybenzylidene)-4-butylaniline (MBBA, 1), results in the expulsion of compounds that do not participate in the formation of the liquid crystalline phase. Furthermore, amines and aromatic aldehydes undergo component exchange with the imine by generating constitutional dynamic libraries. The strength of the electric field and the duration of its application to the liquid crystalline film influence the release rate of the expelled compounds and, at the same time, modulate the equilibration of the dynamic libraries. The controlled release of volatile organic molecules with different chemical functionalities from the film was quantified by dynamic headspace analysis. In all cases, higher headspace concentrations were detected in the presence of an electric field. These results point to the possibility of using imine-based liquid crystalline films to build devices for the controlled release of a broad variety of bioactive volatiles as a direct response to an external electric signal.

Dramatically different kinetics and mechanism at solid/liquid and solid/gas interfaces for catalytic isopropanol oxidation over size-controlled platinum nanoparticles.

PubMed

Wang, Hailiang; Sapi, Andras; Thompson, Christopher M; Liu, Fudong; Zherebetskyy, Danylo; Krier, James M; Carl, Lindsay M; Cai, Xiaojun; Wang, Lin-Wang; Somorjai, Gabor A

2014-07-23

We synthesize platinum nanoparticles with controlled average sizes of 2, 4, 6, and 8 nm and use them as model catalysts to study isopropanol oxidation to acetone in both the liquid and gas phases at 60 °C. The reaction at the solid/liquid interface is 2 orders of magnitude slower than that at the solid/gas interface, while catalytic activity increases with the size of platinum nanoparticles for both the liquid-phase and gas-phase reactions. The activation energy of the gas-phase reaction decreases with the platinum nanoparticle size and is in general much higher than that of the liquid-phase reaction which is largely insensitive to the size of catalyst nanoparticles. Water substantially promotes isopropanol oxidation in the liquid phase. However, it inhibits the reaction in the gas phase. The kinetic results suggest different mechanisms between the liquid-phase and gas-phase reactions, correlating well with different orientations of IPA species at the solid/liquid interface vs the solid/gas interface as probed by sum frequency generation vibrational spectroscopy under reaction conditions and simulated by computational calculations.

Equilibrium properties and phase diagram of two-dimensional Yukawa systems

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

Hartmann, P.; Donko, Z.; Kutasi, K.

Properties of two-dimensional strongly coupled Yukawa systems are explored through molecular dynamics simulations. An effective coupling coefficient {gamma}{sup *} for the liquid phase is introduced on the basis of the constancy of the first peak amplitude of the pair-correlation functions. Thermodynamic quantities are calculated from the pair-correlation function. The solid-liquid transition of the system is investigated through the analysis of the bond-angular order parameter. The static structure function satisfies consistency relation, attesting to the reliability of the computational method. The response is shown to be governed by the correlational part of the inverse compressibility. An analysis of the velocity autocorrelationmore » demonstrates that this latter also exhibits a universal behavior.« less

Solid-phase microextraction coupled to liquid chromatography for the analysis of phenolic compounds in water.

PubMed

González-Toledo, E; Prat, M D; Alpendurada, M F

2001-07-20

Solid-phase microextraction (SPME) coupled to high-performance liquid chromatography (HPLC) has been applied to the analysis of priority pollutant phenolic compounds in water samples. Two types of polar fibers [50 microm Carbowax-templated resin (CW-TPR) and 60 microm polydimethylsiloxane-divinylbenzene (PDMS-DVB)] were evaluated. The effects of equilibration time and ionic strength of samples on the adsorption step were studied. The parameters affecting the desorption process, such as desorption mode, solvent composition and desorption time, were optimized. The developed method was used to determine the phenols in spiked river water samples collected in the Douro River, Portugal. Detection limits of 1-10 microg l(-1) were achieved under the optimized conditions.

ON SITE SOLID-PHASE EXTRACTION AND LABORATORY ANALYSIS OF ULTRA-TRACE SYNTHETIC MUSKS IN MUNICIPAL SEWAGE EFFLUENT USING GAS CHROMATOGRAPHY-MASS SPECTROMETRY. FULL-SCAN MODE

EPA Science Inventory

Fragrance materials such as synthetic musks in aqueous samples, are normally determined by gas chromatography/mass spectrometry in the selected ion monitoring (SIM) mode to provide maximum sensitivity after liquid-liquid extraction of I -L samples. Full-scan mass spectra are requ...

Residue analysis of sixty pesticides in red swamp crayfish using QuEChERS with high-performance liquid chromatography-tandem mass spectrometry

USDA-ARS?s Scientific Manuscript database

In this study, a multi-residue analytical method using QuEChERS extraction and dispersive solid-phase extraction (d-SPE) cleanup followed by high-performance liquid chromatography–tandem mass spectrometry (HPLC-MS/MS) was developed for rapid determination of 60 pesticide residues in whole crayfish a...

Analysis of human serum proteins by liquid phase isoelectric focusing and matrix-assisted laser desorption/ionization-mass spectrometry.

PubMed

Wang, Michael Z; Howard, Brandon; Campa, Michael J; Patz, Edward F; Fitzgerald, Michael C

2003-09-01

Direct matrix-assisted laser desorption/ionization-time of flight mass spectrometry (MALDI-TOF MS) analysis of human serum yielded ion signals from only a fraction of the total number of peptides and proteins expected to be in the sample. We increased the number of peptide and protein ion signals observed in the MALDI-TOF mass spectra analysis of human serum by using a prefractionation protocol based on liquid phase isoelectric focusing electrophoresis. This pre-fractionation technique facilitated the MALDI-TOF MS detection of as many as 262 different peptide and protein ion signals from human serum. The results obtained from three replicate fractionation experiments on the same serum sample indicated that 148 different peptide and protein ion signals were reproducibly detected using our isoelectric focusing and MALDI-TOF MS protocol.

Universal Behavior of Quantum Spin Liquid and Optical Conductivity in the Insulator Herbertsmithite

NASA Astrophysics Data System (ADS)

Shaginyan, V. R.; Msezane, A. Z.; Stephanovich, V. A.; Popov, K. G.; Japaridze, G. S.

2018-04-01

We analyze optical conductivity with the goal to demonstrate experimental manifestation of a new state of matter, the so-called fermion condensate. Fermion condensates are realized in quantum spin liquids, exhibiting typical behavior of heavy-fermion metals. Measurements of the low-frequency optical conductivity collected on the geometrically frustrated insulator herbertsmithite provide important experimental evidence of the nature of its quantum spin liquid composed of spinons. To analyze recent measurements of the herbertsmithite optical conductivity at different temperatures, we employ a model of strongly correlated quantum spin liquid located near the fermion condensation phase transition. Our theoretical analysis of the optical conductivity allows us to expose the physical mechanism of its temperature dependence. We also predict a dependence of the optical conductivity on a magnetic field. We consider an experimental manifestation (optical conductivity) of a new state of matter (so-called fermion condensate) realized in quantum spin liquids, for, in many ways, they exhibit typical behavior of heavy-fermion metals. Measurements of the low-frequency optical conductivity collected on the geometrically frustrated insulator herbertsmithite produce important experimental evidence of the nature of its quantum spin liquid composed of spinons. To analyze recent measurements of the herbertsmithite optical conductivity at different temperatures, we employ a model of a strongly correlated quantum spin liquid located near the fermion condensation phase transition. Our theoretical analysis of the optical conductivity allows us to reveal the physical mechanism of its temperature dependence. We also predict a dependence of the optical conductivity on a magnetic field.

Analysis of Two-Phase Flow in Damper Seals for Cryogenic Turbopumps

NASA Technical Reports Server (NTRS)

Arauz, Grigory L.; SanAndres, Luis

1996-01-01

Cryogenic damper seals operating close to the liquid-vapor region (near the critical point or slightly su-cooled) are likely to present two-phase flow conditions. Under single phase flow conditions the mechanical energy conveyed to the fluid increases its temperature and causes a phase change when the fluid temperature reaches the saturation value. A bulk-flow analysis for the prediction of the dynamic force response of damper seals operating under two-phase conditions is presented as: all-liquid, liquid-vapor, and all-vapor, i.e. a 'continuous vaporization' model. The two phase region is considered as a homogeneous saturated mixture in thermodynamic equilibrium. Th flow in each region is described by continuity, momentum and energy transport equations. The interdependency of fluid temperatures and pressure in the two-phase region (saturated mixture) does not allow the use of an energy equation in terms of fluid temperature. Instead, the energy transport is expressed in terms of fluid enthalpy. Temperature in the single phase regions, or mixture composition in the two phase region are determined based on the fluid enthalpy. The flow is also regarded as adiabatic since the large axial velocities typical of the seal application determine small levels of heat conduction to the walls as compared to the heat carried by fluid advection. Static and dynamic force characteristics for the seal are obtained from a perturbation analysis of the governing equations. The solution expressed in terms of zeroth and first order fields provide the static (leakage, torque, velocity, pressure, temperature, and mixture composition fields) and dynamic (rotordynamic force coefficients) seal parameters. Theoretical predictions show good agreement with experimental leakage pressure profiles, available from a Nitrogen at cryogenic temperatures. Force coefficient predictions for two phase flow conditions show significant fluid compressibility effects, particularly for mixtures with low mass content of vapor. Under these conditions, an increase on direct stiffness and reduction of whirl frequency ratio are shown to occur. Prediction of such important effects will motivate experimental studies as well as a more judicious selection of the operating conditions for seals used in cryogenic turbomachinery.

Phase-partitioning in mixed-phase clouds - An approach to characterize the entire vertical column

NASA Astrophysics Data System (ADS)

Kalesse, H.; Luke, E. P.; Seifert, P.

2017-12-01

The characterization of the entire vertical profile of phase-partitioning in mixed-phase clouds is a challenge which can be addressed by synergistic profiling measurements with ground-based polarization lidars and cloud radars. While lidars are sensitive to small particles and can thus detect supercooled liquid (SCL) layers, cloud radar returns are dominated by larger particles (like ice crystals). The maximum lidar observation height is determined by complete signal attenuation at a penetrated optical depth of about three. In contrast, cloud radars are able to penetrate multiple liquid layers and can thus be used to expand the identification of cloud phase to the entire vertical column beyond the lidar extinction height, if morphological features in the radar Doppler spectrum can be related to the existence of SCL. Relevant spectral signatures such as bimodalities and spectral skewness can be related to cloud phase by training a neural network appropriately in a supervised learning scheme, with lidar measurements functioning as supervisor. The neural network output (prediction of SCL location) derived using cloud radar Doppler spectra can be evaluated with several parameters such as liquid water path (LWP) detected by microwave radiometer (MWR) and (liquid) cloud base detected by ceilometer or Raman lidar. The technique has been previously tested on data from Department of Energy (DOE) Atmospheric Radiation Measurement (ARM) instruments in Barrow, Alaska and is in this study utilized for observations from the Leipzig Aerosol and Cloud Remote Observations System (LACROS) during the Analysis of the Composition of Clouds with Extended Polarization Techniques (ACCEPT) field experiment in Cabauw, Netherlands in Fall 2014. Comparisons to supercooled-liquid layers as classified by CLOUDNET are provided.

Simultaneous analysis of carotenoids and tocopherols in botanical species using one step solid-liquid extraction followed by high performance liquid chromatography.

PubMed

Valdivielso, Izaskun; Bustamante, María Ángeles; Ruiz de Gordoa, Juan Carlos; Nájera, Ana Isabel; de Renobales, Mertxe; Barron, Luis Javier R

2015-04-15

Carotenoids and tocopherols from botanical species abundant in Atlantic mountain grasslands were simultaneously extracted using one-step solid-liquid phase. A single n-hexane/2-propanol extract containing both types of compounds was injected twice under two different sets of HPLC conditions to separate the tocopherols by normal-phase chromatography and carotenoids by reverse-phase mode. The method allowed reproducible quantification in plant samples of very low amounts of α-, β-, γ- and δ-tocopherols (LOD from 0.0379 to 0.0720 μg g(-1) DM) and over 15 different xanthophylls and carotene isomers. The simplified one-step extraction without saponification significantly increased the recovery of tocopherols and carotenoids, thereby enabling the determination of α-tocopherol acetate in plant samples. The two different sets of chromatographic analysis provided near baseline separation of individual compounds without interference from other lipid compounds extracted from plants, and a very sensitive and accurate detection of tocopherols and carotenoids. The detection of minor individual components in botanical species from grasslands is nowadays of high interest in searching for biomarkers for foods derived from grazing animals. Copyright © 2014 Elsevier Ltd. All rights reserved.

Quantitative Analysis of Tetramethylenedisulfotetramine ("Tetramine") Spiked into Beverages by Liquid Chromatography Tandem Mass Spectrometry with Validation by Gas Chromatography Mass Spectrometry

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

Owens, J; Hok, S; Alcaraz, A

Tetramethylenedisulfotetramine, commonly known as tetramine, is a highly neurotoxic rodenticide (human oral LD{sub 50} = 0.1 mg/kg) used in hundreds of deliberate food poisoning events in China. Here we describe a method for quantitation of tetramine spiked into beverages, including milk, juice, tea, cola, and water and cleaned up by C8 solid phase extraction and liquid-liquid extraction. Quantitation by high performance liquid chromatography tandem mass spectrometry (LC/MS/MS) was based upon fragmentation of m/z 347 to m/z 268. The method was validated by gas chromatography mass spectrometry (GC/MS) operated in SIM mode for ions m/z 212, 240, and 360. The limitmore » of quantitation was 0.10 {micro}g/mL by LC/MS/MS versus 0.15 {micro}g/mL for GC/MS. Fortifications of the beverages at 2.5 {micro}g/mL and 0.25 {micro}g/mL were recovered ranging from 73-128% by liquid-liquid extraction for GC/MS analysis, 13-96% by SPE and 10-101% by liquid-liquid extraction for LC/MS/MS analysis.« less

On the accuracy of the MB-pol many-body potential for water: Interaction energies, vibrational frequencies, and classical thermodynamic and dynamical properties from clusters to liquid water and ice

NASA Astrophysics Data System (ADS)

Reddy, Sandeep K.; Straight, Shelby C.; Bajaj, Pushp; Huy Pham, C.; Riera, Marc; Moberg, Daniel R.; Morales, Miguel A.; Knight, Chris; Götz, Andreas W.; Paesani, Francesco

2016-11-01

The MB-pol many-body potential has recently emerged as an accurate molecular model for water simulations from the gas to the condensed phase. In this study, the accuracy of MB-pol is systematically assessed across the three phases of water through extensive comparisons with experimental data and high-level ab initio calculations. Individual many-body contributions to the interaction energies as well as vibrational spectra of water clusters calculated with MB-pol are in excellent agreement with reference data obtained at the coupled cluster level. Several structural, thermodynamic, and dynamical properties of the liquid phase at atmospheric pressure are investigated through classical molecular dynamics simulations as a function of temperature. The structural properties of the liquid phase are in nearly quantitative agreement with X-ray diffraction data available over the temperature range from 268 to 368 K. The analysis of other thermodynamic and dynamical quantities emphasizes the importance of explicitly including nuclear quantum effects in the simulations, especially at low temperature, for a physically correct description of the properties of liquid water. Furthermore, both densities and lattice energies of several ice phases are also correctly reproduced by MB-pol. Following a recent study of DFT models for water, a score is assigned to each computed property, which demonstrates the high and, in many respects, unprecedented accuracy of MB-pol in representing all three phases of water.

Determination of spirocyclic tetronic/tetramic acid derivatives and neonicotinoid insecticides in fruits and vegetables by liquid chromatography and mass spectrometry after dispersive liquid-liquid microextraction.

PubMed

Pastor-Belda, Marta; Garrido, Isabel; Campillo, Natalia; Viñas, Pilar; Hellín, Pilar; Flores, Pilar; Fenoll, José

2016-07-01

Dispersive liquid-liquid microextraction was used to preconcentrate three spirocyclic tetronic/tetramic acid derivatives (spirotetramat, spiromesifen and spirodiclofen) and five neonicotinoid (thiamethoxam, chlotianidin, imidacloprid, acetamiprid and thiacloprid) insecticides previously extracted from fruit and vegetable matrices with acetonitrile. The organic enriched phase was evaporated, reconstituted in 25μL acetonitrile and analyzed by reversed-phase liquid chromatography with tandem mass spectrometry using a triple quadrupole in selected reaction monitoring mode. Enrichment factors in the 15-100 range were obtained. A matrix effect was observed, the detection limits varying between 0.025 and 0.5ngg(-1), depending on the compound and the sample matrix. The developed method was applied to the analysis of 25 samples corresponding to five different fruit and vegetable matrices. Only thiamethoxam was detected in a lemon sample at a concentration close to the quantification limit, and spiromesifen and spirotetramat at concentrations between 11.6 and 54.5ngg(-1). Copyright © 2016 Elsevier Ltd. All rights reserved.

Optimisation of ultrasound-assisted reverse micelles dispersive liquid-liquid micro-extraction by Box-Behnken design for determination of acetoin in butter followed by high performance liquid chromatography.

PubMed

Roosta, Mostafa; Ghaedi, Mehrorang; Daneshfar, Ali

2014-10-15

A novel approach, ultrasound-assisted reverse micelles dispersive liquid-liquid microextraction (USA-RM-DLLME) followed by high performance liquid chromatography (HPLC) was developed for selective determination of acetoin in butter. The melted butter sample was diluted and homogenised by n-hexane and Triton X-100, respectively. Subsequently, 400μL of distilled water was added and the microextraction was accelerated by 4min sonication. After 8.5min of centrifugation, sedimented phase (surfactant-rich phase) was withdrawn by microsyringe and injected into the HPLC system for analysis. The influence of effective variables was optimised using Box-Behnken design (BBD) combined with desirability function (DF). Under optimised experimental conditions, the calibration graph was linear over the range of 0.6-200mgL(-1). The detection limit of method was 0.2mgL(-1) and coefficient of determination was 0.9992. The relative standard deviations (RSDs) were less than 5% (n=5) while the recoveries were in the range of 93.9-107.8%. Copyright © 2014. Published by Elsevier Ltd.

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

Solution for blank and matrix difficulties encountered during phthalate analysis of edible oils by high performance liquid chromatography coupled with tandem mass spectrometry.

PubMed

Vavrouš, Adam; Pavloušková, Jana; Ševčík, Václav; Vrbík, Karel; Čabala, Radomír

2016-07-22

Worldwide production of phthalates has led to their undesirable presence in the food chain. Particularly edible oils have become an area of growing concern owing to numerous reported occurrences of phthalates. The analytical methods used in this field face difficulties associated mainly with matrix complexity or phthalate contamination which this study has aimed to describe and resolve. The proposed procedure consisting of liquid-liquid extraction, solid phase extraction and high performance liquid chromatography coupled with tandem mass spectrometry allowed us to analyze simultaneously 6 individual phthalates and 2 phthalate isomeric mixtures. DSC-18 SPE phase was selected for cleanup owing to the most efficient co-extract removal (assessed using high resolution mass spectrometry). Several sources of phthalate contamination were identified, however, the mobile phase was the most serious. The key improvement was achieved by equipping a contamination trap, a 50-mm reverse phase HPLC column, generating a delay between target and mobile phase peaks of the same compounds. RSDs ranging between 2.4 and 16 % confirm good precision and LOQs between 5.5 and 110μgkg(-1) reflect satisfactory blank management. With up to 19 occurrences in 25 analyzed edible oil samples and levels up to 33mgkg(-1), bis(2-ethylhexyl), diisononyl and diisodecyl phthalates were the most important contaminants. Copyright © 2016 Elsevier B.V. All rights reserved.

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

PubMed

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

2015-06-01

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

A Generalized Eulerian-Lagrangian Analysis, with Application to Liquid Flows with Vapor Bubbles

NASA Technical Reports Server (NTRS)

Dejong, Frederik J.; Meyyappan, Meyya

1993-01-01

Under a NASA MSFC SBIR Phase 2 effort an analysis has been developed for liquid flows with vapor bubbles such as those in liquid rocket engine components. The analysis is based on a combined Eulerian-Lagrangian technique, in which Eulerian conservation equations are solved for the liquid phase, while Lagrangian equations of motion are integrated in computational coordinates for the vapor phase. The novel aspect of the Lagrangian analysis developed under this effort is that it combines features of the so-called particle distribution approach with those of the so-called particle trajectory approach and can, in fact, be considered as a generalization of both of those traditional methods. The result of this generalization is a reduction in CPU time and memory requirements. Particle time step (stability) limitations have been eliminated by semi-implicit integration of the particle equations of motion (and, for certain applications, the particle temperature equation), although practical limitations remain in effect for reasons of accuracy. The analysis has been applied to the simulation of cavitating flow through a single-bladed section of a labyrinth seal. Models for the simulation of bubble formation and growth have been included, as well as models for bubble drag and heat transfer. The results indicate that bubble formation is more or less 'explosive'. for a given flow field, the number density of bubble nucleation sites is very sensitive to the vapor properties and the surface tension. The bubble motion, on the other hand, is much less sensitive to the properties, but is affected strongly by the local pressure gradients in the flow field. In situations where either the material properties or the flow field are not known with sufficient accuracy, parametric studies can be carried out rapidly to assess the effect of the important variables. Future work will include application of the analysis to cavitation in inducer flow fields.

Method for removing solid particulate material from within liquid fuel injector assemblies

DOEpatents

Simandl, R.F.; Brown, J.D.; Andriulli, J.B.; Strain, P.D.

1998-09-08

A method is described for removing residual solid particulate material from the interior of liquid fuel injectors and other fluid flow control mechanisms having or being operatively associated with a flow-regulating fixed or variable orifice. The method comprises the sequential and alternate introduction of columns of a non-compressible liquid phase and columns of a compressed gas phase into the body of a fuel injector whereby the expansion of each column of the gas phase across the orifice accelerates the liquid phase in each trailing column of the liquid phase and thereby generates turbulence in each liquid phase for lifting and entraining the solid particulates for the subsequent removal thereof from the body of the fuel injector. 1 fig.

Method for removing solid particulate material from within liquid fuel injector assemblies

DOEpatents

Simandl, Ronald F.; Brown, John D.; Andriulli, John B.; Strain, Paul D.

1998-01-01

A method for removing residual solid particulate material from the interior of liquid fuel injectors and other fluid flow control mechanisms having or being operatively associated with a flow-regulating fixed or variable orifice. The method comprises the sequential and alternate introduction of columns of a non-compressible liquid phase and columns of a compressed gas phase into the body of a fuel injector whereby the expansion of each column of the gas phase across the orifice accelerates the liquid phase in each trailing column of the liquid phase and thereby generates turbulence in each liquid phase for lifting and entraining the solid particulates for the subsequent removal thereof from the body of the fuel injector.

Complex Fluids at Interfaces and Interfaces of Complex Fluids

NASA Astrophysics Data System (ADS)

Nouri, Mariam

The present thesis deals with two independent projects and is consequently divided into two parts. The first part details a computational study of the fluid structure of ring-shaped molecules and their positional and orientational molecular organizations in different degrees of confinement, while the second part concerns an experimental study of phase behavior and interfacial phenomena in confined colloid-polymer systems. In the first part, ring-shaped molecules are studied using Monte Carlo simulation techniques in one, two and three dimensions. The model used to describe ring-shaped molecules is composed of hard-spheres linked together to form planar rigid rings. For rings of various sizes and for a wide range of densities, positional and orientational orderings are reported in forms of pair distribution functions of the ring centers and correlation functions of the ring normal orientations. Special emphasis is given to understand structural formation at interfaces, i.e., the structure and orderings of these molecules when they are confined to two dimensions. In a plane but the rings themselves are free to rotate around all axes, nematic ordering is observed at sufficiently high densities. In the second part, phase equilibria of confined aqueous colloid-polymer systems are studied experimentally using fluorescence microscopy. Aqueous mixtures of fluorescent polystyrene spheres and polyacrylamide are confined between a glass slide and a coverslip. The phase diagram is determined as a function of the colloidal and polymer concentrations. Liquid-liquid phase coexistence between a colloid-rich phase and a polymer-rich phase occurs at intermediate polymer concentrations, while liquid-solid phase coexistence between a polymer-rich liquid and a colloid-rich solid is observed at high polymer concentrations. Interfacial thickness and tension of the interface between these coexisting phases are measured using image analysis techniques. It is also observed that the colloid-rich solid and liquid domains coarsen mainly by Ostwald ripening.

DYNAMIC MODELING STRATEGY FOR FLOW REGIME TRANSITION IN GAS-LIQUID TWO-PHASE FLOWS

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

X. Wang; X. Sun; H. Zhao

In modeling gas-liquid two-phase flows, the concept of flow regime has been used to characterize the global interfacial structure of the flows. Nearly all constitutive relations that provide closures to the interfacial transfers in two-phase flow models, such as the two-fluid model, are often flow regime dependent. Currently, the determination of the flow regimes is primarily based on flow regime maps or transition criteria, which are developed for steady-state, fully-developed flows and widely applied in nuclear reactor system safety analysis codes, such as RELAP5. As two-phase flows are observed to be dynamic in nature (fully-developed two-phase flows generally do notmore » exist in real applications), it is of importance to model the flow regime transition dynamically for more accurate predictions of two-phase flows. The present work aims to develop a dynamic modeling strategy for determining flow regimes in gas-liquid two-phase flows through the introduction of interfacial area transport equations (IATEs) within the framework of a two-fluid model. The IATE is a transport equation that models the interfacial area concentration by considering the creation and destruction of the interfacial area, such as the fluid particle (bubble or liquid droplet) disintegration, boiling and evaporation; and fluid particle coalescence and condensation, respectively. For the flow regimes beyond bubbly flows, a two-group IATE has been proposed, in which bubbles are divided into two groups based on their size and shape (which are correlated), namely small bubbles and large bubbles. A preliminary approach to dynamically identifying the flow regimes is provided, in which discriminators are based on the predicted information, such as the void fraction and interfacial area concentration of small bubble and large bubble groups. This method is expected to be applied to computer codes to improve their predictive capabilities of gas-liquid two-phase flows, in particular for the applications in which flow regime transition occurs.« less

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.

Combining Laser Ablation/Liquid Phase Collection Surface Sampling and High-Performance Liquid Chromatography Electrospray Ionization Mass Spectrometry

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

Ovchinnikova, Olga S; Kertesz, Vilmos; Van Berkel, Gary J

This paper describes the coupling of ambient pressure transmission geometry laser ablation with a liquid phase sample collection method for surface sampling and ionization with subsequent mass spectral analysis. A commercially available autosampler was adapted to produce a liquid droplet at the end of the syringe injection needle while in close proximity to the surface to collect the sample plume produced by laser ablation. The sample collection was followed by either flow injection or a high performance liquid chromatography (HPLC) separation of the extracted components and detection with electrospray ionization mass spectrometry (ESI-MS). To illustrate the analytical utility of thismore » coupling, thin films of a commercial ink sample containing rhodamine 6G and of mixed isobaric rhodamine B and 6G dyes on glass microscope slides were analyzed. The flow injection and HPLC/ESI-MS analysis revealed successful laser ablation, capture and, with HPLC, the separation of the two compounds. The ablated circular area was about 70 m in diameter for these experiments. The spatial sampling resolution afforded by the laser ablation, as well as the ability to use sample processing methods like HPLC between the sample collection and ionization steps, makes this combined surface sampling/ionization technique a highly versatile analytical tool.« less

MUFITS Code for Modeling Geological Storage of Carbon Dioxide at Sub- and Supercritical Conditions

NASA Astrophysics Data System (ADS)

Afanasyev, A.

2012-12-01

Two-phase models are widely used for simulation of CO2 storage in saline aquifers. These models support gaseous phase mainly saturated with CO2 and liquid phase mainly saturated with H2O (e.g. TOUGH2 code). The models can be applied to analysis of CO2 storage only in relatively deeply-buried reservoirs where pressure exceeds CO2 critical pressure. At these supercritical reservoir conditions only one supercritical CO2-rich phase appears in aquifer due to CO2 injection. In shallow aquifers where reservoir pressure is less than the critical pressure CO2 can split in two different liquid-like and gas-like phases (e.g. Spycher et al., 2003). Thus a region of three-phase flow of water, liquid and gaseous CO2 can appear near the CO2 injection point. Today there is no widely used and generally accepted numerical model capable of the three-phase flows with two CO2-rich phases. In this work we propose a new hydrodynamic simulator MUFITS (Multiphase Filtration Transport Simulator) for multiphase compositional modeling of CO2-H2O mixture flows in porous media at conditions of interest for carbon sequestration. The simulator is effective both for supercritical flows in a wide range of pressure and temperature and for subcritical three-phase flows of water, liquid CO2 and gaseous CO2 in shallow reservoirs. The distinctive feature of the proposed code lies in the methodology for mixture properties determination. Transport equations and Darcy correlation are solved together with calculation of the entropy maximum that is reached in thermodynamic equilibrium and determines the mixture composition. To define and solve the problem only one function - mixture thermodynamic potential - is required. The potential is determined using a three-parametric generalization of Peng-Robinson equation of state fitted to experimental data (Todheide, Takenouchi, Altunin etc.). We apply MUFITS to simple 1D and 2D test problems of CO2 injection in shallow reservoirs subjected to phase changes between liquid and gaseous CO2. We consider CO2 injection into highly heterogeneous the 10th SPE reservoir. We provide analysis of physical phenomena that have control temperature distribution in the reservoir. The distribution is non-monotonic with regions of high and low temperature. The main phenomena responsible for considerable temperature decline around CO2 injection point is the liquid CO2 evaporation process. We also apply the code to real-scale 3D simulations of CO2 geological storage at supercritical conditions in Sleipner field and Johansen formation (Fig). The work is supported financially by the Russian Foundation for Basic Research (12-01-31117) and grant for leading scientific schools (NSh 1303.2012.1). CO2 phase saturation in Johansen formation after 50 years of injection and 1000 years of rest period

A review of solid-fluid selection options for optical-based measurements in single-phase liquid, two-phase liquid-liquid and multiphase solid-liquid flows

NASA Astrophysics Data System (ADS)

Wright, Stuart F.; Zadrazil, Ivan; Markides, Christos N.

2017-09-01

Experimental techniques based on optical measurement principles have experienced significant growth in recent decades. They are able to provide detailed information with high-spatiotemporal resolution on important scalar (e.g., temperature, concentration, and phase) and vector (e.g., velocity) fields in single-phase or multiphase flows, as well as interfacial characteristics in the latter, which has been instrumental to step-changes in our fundamental understanding of these flows, and the development and validation of advanced models with ever-improving predictive accuracy and reliability. Relevant techniques rely upon well-established optical methods such as direct photography, laser-induced fluorescence, laser Doppler velocimetry/phase Doppler anemometry, particle image/tracking velocimetry, and variants thereof. The accuracy of the resulting data depends on numerous factors including, importantly, the refractive indices of the solids and liquids used. The best results are obtained when the observational materials have closely matched refractive indices, including test-section walls, liquid phases, and any suspended particles. This paper reviews solid-liquid and solid-liquid-liquid refractive-index-matched systems employed in different fields, e.g., multiphase flows, turbomachinery, bio-fluid flows, with an emphasis on liquid-liquid systems. The refractive indices of various aqueous and organic phases found in the literature span the range 1.330-1.620 and 1.251-1.637, respectively, allowing the identification of appropriate combinations to match selected transparent or translucent plastics/polymers, glasses, or custom materials in single-phase liquid or multiphase liquid-liquid flow systems. In addition, the refractive indices of fluids can be further tuned with the use of additives, which also allows for the matching of important flow similarity parameters such as density and viscosity.

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

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.

Solid phase pegylation of hemoglobin.

PubMed

Suo, Xiaoyan; Zheng, Chunyang; Yu, Pengzhan; Lu, Xiuling; Ma, Guanghui; Su, Zhiguo

2009-01-01

A solid phase conjugation process was developed for attachment of polyethylene glycol to hemoglobin molecule. Bovine hemoglobin was loaded onto an ion exchange chromatography column and adsorbed by the solid medium. Succinimidyl carbonate mPEG was introduced in the mobile phase after the adsorption. Pegylation took place between the hemoglobin on the solid phase, and the pegylation reagent in the liquid phase. A further elution was carried out to separate the pegylated and the unpegylated protein. Analysis by HPSEC, SDS-PAGE, and MALLS demonstrated that the fractions eluted from the solid phase contained well-defined components. Pegylated hemoglobin with one PEG chain was obtained with the yield of 75%, in comparison to the yield of 30% in the liquid phase pegylation. The P(50) values of the mono-pegylated hemoglobin, prepared with SC-mPEG 5 kDa, 10 kDa and 20 kDa, were 19.97, 20.23 and 20.54 mmHg, which were much closer to the value of red blood cells than that of pegylated hemoglobin prepared with the conventional method.

Theoretical analysis for double-liquid variable focus lens

NASA Astrophysics Data System (ADS)

Peng, Runling; Chen, Jiabi; Zhuang, Songlin

2007-09-01

In this paper, various structures for double-liquid variable focus lens are introduced. And based on an energy minimization method, explicit calculations and detailed analyses upon an extended Young-type equation are given for double-liquid lenses with cylindrical electrode. Such an equation is especially applicable to liquid-liquid-solid tri-phase systems. It is a little different from the traditional Young equation that was derived according to vapor-liquid-solid triphase systems. The electrowetting effect caused by an external voltage changes the interface shape between two liquids as well as the focal length of the lens. Based on the extended Young-type equation, the relationship between the focal length and the external voltage can also be derived. Corresponding equations and simulation results are presented.

Quantitative ionspray liquid chromatographic/tandem mass spectrometric determination of reserpine in equine plasma.

PubMed

Anderson, M A; Wachs, T; Henion, J D

1997-02-01

A method based on ionspray liquid chromatography/tandem mass spectrometry (LC/MS/MS) was developed for the determination of reserpine in equine plasma. A comparison was made of the isolation of reserpine from plasma by liquid-liquid extraction and by solid-phase extraction. A structural analog, rescinnamine, was used as the internal standard. The reconstituted extracts were analyzed by ionspray LC/MS/MS in the selected reaction monitoring (SRM) mode. The calibration graph for reserpine extracted from equine plasma obtained using liquid-liquid extraction was linear from 10 to 5000 pg ml-1 and that using solid-phase extraction from 100 to 5000 pg ml-1. The lower level of quantitation (LLQ) using liquid-liquid and solid-phase extraction was 50 and 200 pg ml-1, respectively. The lower level of detection for reserpine by LC/MS/MS was 10 pg ml-1. The intra-assay accuracy did not exceed 13% for liquid-liquid and 12% for solid-phase extraction. The recoveries for the LLQ were 68% for liquid-liquid and 58% for solid-phase extraction.

High-throughput method for macrolides and lincosamides antibiotics residues analysis in milk and muscle using a simple liquid-liquid extraction technique and liquid chromatography-electrospray-tandem mass spectrometry analysis (LC-MS/MS).

PubMed

Jank, Louise; Martins, Magda Targa; Arsand, Juliana Bazzan; Campos Motta, Tanara Magalhães; Hoff, Rodrigo Barcellos; Barreto, Fabiano; Pizzolato, Tânia Mara

2015-11-01

A fast and simple method for residue analysis of the antibiotics classes of macrolides (erythromycin, azithromycin, tylosin, tilmicosin and spiramycin) and lincosamides (lincomycin and clindamycin) was developed and validated for cattle, swine and chicken muscle and for bovine milk. Sample preparation consists in a liquid-liquid extraction (LLE) with acetonitrile, followed by liquid chromatography-electrospray-tandem mass spectrometry analysis (LC-ESI-MS/MS), without the need of any additional clean-up steps. Chromatographic separation was achieved using a C18 column and a mobile phase composed by acidified acetonitrile and water. The method was fully validated according the criteria of the Commission Decision 2002/657/EC. Validation parameters such as limit of detection, limit of quantification, linearity, accuracy, repeatability, specificity, reproducibility, decision limit (CCα) and detection capability (CCβ) were evaluated. All calculated values met the established criteria. Reproducibility values, expressed as coefficient of variation, were all lower than 19.1%. Recoveries range from 60% to 107%. Limits of detection were from 5 to 25 µg kg(-1).The present method is able to be applied in routine analysis, with adequate time of analysis, low cost and a simple sample preparation protocol. Copyright © 2015. Published by Elsevier B.V.

X-ray computed microtomography of sea ice - comment on "A review of air-ice chemical and physical interactions (AICI): liquids, quasi-liquids, and solids in snow" by Bartels-Rausch et al. (2014)

NASA Astrophysics Data System (ADS)

Obbard, R. W.

2015-07-01

This comment addresses a statement made in "A review of air-ice chemical and physical interactions (AICI): liquids, quasi-liquids, and solids in snow" by Bartels-Rausch et al. (Atmos. Chem. Phys., 14, 1587-1633, doi:10.5194/acp-14-1587-2014, 2014). Here we rebut the assertion that X-ray computed microtomography of sea ice fails to reveal liquid brine inclusions by discussing the phases present at the analysis temperature.

Evaluation of the pathways of tropospheric nitrophenol formation using a multiphase model

NASA Astrophysics Data System (ADS)

Harrison, M. A. J.; Heal, M. R.; Cape, J. N.

2005-03-01

Phenols are a major class of volatile organic compounds (VOC) whose reaction within, and partitioning between, the gas and liquid phases affects their lifetime within the atmosphere, the local oxidising capacity, and the extent of production of nitrophenols, which are toxic chemicals. In this work, a zero-dimension box model was constructed to quantify the relative nitration pathways, and partitioning into the liquid phase, of mono-aromatic compounds in order to help elucidate the formation pathways of 2- and 4-nitrophenol in the troposphere. The liquid phase contributed significantly to the production of nitrophenols for liquid water content (Lc) values exceeding 3×10-9, and for a range of assumed liquid droplet diameter, even though the resultant equilibrium partitioning to the liquid phase was much lower. For example, in a ''typical'' model scenario, with Lc=3×10-7, 58% of nitrophenol production occurred in the liquid phase but only 2% of nitrophenol remained there, i.e. a significant proportion of nitrophenol observed in the gas phase may actually be produced via the liquid phase. The importance of the liquid phase was enhanced at lower temperatures, by a factor ~1.5-2 at 278 K cf. 298 K. The model showed that nitrophenol production was particularly sensitive to the values of the rate coefficients for the liquid phase reactions between phenol and OH or NO3 reactions, but insensitive to the rate coefficient for the reaction between benzene and OH, thus identifying where further experimental data are required.

Comprehensive hydrophilic interaction and ion-pair reversed-phase liquid chromatography for analysis of di- to deca-oligonucleotides.

PubMed

Li, Qin; Lynen, Frédéric; Wang, Jian; Li, Hanlin; Xu, Guowang; Sandra, Pat

2012-09-14

A comprehensive two-dimensional HPLC approach with a high degree of orthogonality was developed for analysis of di- to deca-oligonucleotides (ONs). Hydrophilic interaction liquid chromatography (HILIC) was used in the first dimension, and ion-pair reversed-phase liquid chromatography (IP-RPLC) was employed in the second dimension. The two dimensions were connected via a ten-port valve interface equipped with octadecyl silica (ODS) traps to immobilize and focus the ONs eluting from the first dimension prior to IP-RPLC separation. An aqueous make-up flow was used for effective trapping. The comprehensive two-dimensional HPLC system was optimized with a mixture consisting of 27 oligonucleotide standards. An overall chromatographic peak capacity of 500 was obtained. The use of the volatile buffer triethylamine acetate in the second dimension allowed straightforward coupling to electrospray ionization mass spectrometry (ESI-MS) and detection of each ON in the negative ionization mode. Copyright © 2011 Elsevier B.V. All rights reserved.

Evaluation of a headspace solid-phase microextraction method for the analysis of ignitable liquids in fire debris.

PubMed

Fettig, Ina; Krüger, Simone; Deubel, Jan H; Werrel, Martin; Raspe, Tina; Piechotta, Christian

2014-05-01

The chemical analysis of fire debris represents a crucial part in fire investigations to determine the cause of a fire. A headspace solid-phase microextraction (HS-SPME) procedure for the detection of ignitable liquids in fire debris using a fiber coated with a mixture of three different sorbent materials (Divinylbenzene/Carboxen/Polydimethylsiloxane, DVB/CAR/PDMS) is described. Gasoline and diesel fuel were spiked upon a preburnt matrix (wood charcoal), extracted and concentrated with HS-SPME and then analyzed with gas chromatography/mass spectrometry (GC/MS). The experimental conditions--extraction temperature, incubation and exposure time--were optimized. To assess the applicability of the method, fire debris samples were prepared in the smoke density chamber (SDC) and a controlled-atmosphere cone calorimeter. The developed methods were successfully applied to burnt particleboard and carpet samples. The results demonstrate that the procedure that has been developed here is suitable for detecting these ignitable liquids in highly burnt debris. © 2013 American Academy of Forensic Sciences.

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.

Trace determination of five triazole fungicide residues in traditional Chinese medicine samples by dispersive solid-phase extraction combined with ultrasound-assisted dispersive liquid-liquid microextraction and UHPLC-MS/MS.

PubMed

Ma, Shuping; Yuan, Xucan; Zhao, Pengfei; Sun, Hong; Ye, Xiu; Liang, Ning; Zhao, Longshan

2017-08-01

A novel and reliable method for determination of five triazole fungicide residues (triadimenol, tebuconazole, diniconazole, flutriafol, and hexaconazol) in traditional Chinese medicine samples was developed using dispersive solid-phase extraction combined with ultrasound-assisted dispersive liquid-liquid microextraction before ultra-high performance liquid chromatography with tandem mass spectrometry. The clean up of the extract was conducted using dispersive solid-phase extraction by directly adding sorbents into the extraction solution, followed by shaking and centrifugation. After that, a mixture of 400 μL trichloromethane (extraction solvent) and 0.5 mL of the above supernatant was injected rapidly into water for the dispersive liquid-liquid microextraction procedure. The factors affecting the extraction efficiency were optimized. Under the optimum conditions, the calibration curves showed good linearity in the range of 2.0-400 (tebuconazole, diniconazole, and hexaconazole) and 4.0-800 ng/g (triadimenol and flutriafol) with the regression coefficients higher than 0.9958. The limit of detection and limit of quantification for the present method were 0.5-1.1 and 1.8-4.0 ng/g, respectively. The recoveries of the target analytes ranged from 80.2 to 103.2%. The proposed method has been successfully applied to the analysis of five triazole fungicides in traditional Chinese medicine samples, and satisfactory results were obtained. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Dispersive solid-phase extraction followed by vortex-assisted dispersive liquid-liquid microextraction based on the solidification of a floating organic droplet for the determination of benzoylurea insecticides in soil and sewage sludge.

PubMed

Peng, Guilong; He, Qiang; Mmereki, Daniel; Lu, Ying; Zhong, Zhihui; Liu, Hanyang; Pan, Weiliang; Zhou, Guangming; Chen, Junhua

2016-04-01

A novel dispersive solid-phase extraction combined with vortex-assisted dispersive liquid-liquid microextraction based on solidification of floating organic droplet was developed for the determination of eight benzoylurea insecticides in soil and sewage sludge samples before high-performance liquid chromatography with ultraviolet detection. The analytes were first extracted from the soil and sludge samples into acetone under optimized pretreatment conditions. Clean-up of the extract was conducted by dispersive solid-phase extraction using activated carbon as the sorbent. The vortex-assisted dispersive liquid-liquid microextraction based on solidification of floating organic droplet procedure was performed by using 1-undecanol with lower density than water as the extraction solvent, and the acetone contained in the solution also acted as dispersive solvent. Under the optimum conditions, the linearity of the method was in the range 2-500 ng/g with correlation coefficients (r) of 0.9993-0.9999. The limits of detection were in the range of 0.08-0.56 ng/g. The relative standard deviations varied from 2.16 to 6.26% (n = 5). The enrichment factors ranged from 104 to 118. The extraction recoveries ranged from 81.05 to 97.82% for all of the analytes. The good performance has demonstrated that the proposed methodology has a strong potential for application in the multiresidue analysis of complex matrices. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Simultaneous enantioselective determination of six pesticides in aqueous environmental samples by chiral liquid chromatography with tandem mass spectrometry.

PubMed

Zhao, Pengfei; Lei, Shuo; Xing, Mingming; Xiong, Shihang; Guo, Xingjie

2018-03-01

A robust and sensitive method was developed for the enantiomeric analysis of six chiral pesticides (including metalaxyl, epoxiconazole, myclobutanil, hexaconazole, napropamide, and isocarbophos) in aquatic environmental samples. The optimized chromatographic conditions for the quantification of all the 12 enantiomers were performed with Chiralcel OD-RH column using mobile phase consisting of 0.1% aqueous formic acid and acetonitrile operated under reversed-phase conditions and then analyzed using liquid chromatography with tandem mass spectrometry. Twelve enantiomers were detected in multiple reaction monitoring mode. Solid-phase extraction and dispersive liquid-liquid microextraction were employed in this study. Response surface methodology was applied to assist in the dispersive liquid-liquid microextraction optimization. Under the optimum conditions, recoveries of pesticides enantiomers varied from 83.0 to 103.2% at two spiked levels with relative standard deviation less than 11.5%. The concentration factors were up to 1000 times. Method detection and quantification limits varied from 0.11 to 0.48 ng/L and from 0.46 to 1.49 ng/L, respectively. Finally, this method was used to determination of the enantiomers composition of the six pesticides in environmental aqueous matrices, which will help better understand the behavior of individual enantiomer and make accurate risk assessment to ecosystems. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Competition between Chaotic and Nonchaotic Phases in a Quadratically Coupled Sachdev-Ye-Kitaev Model.

PubMed

Chen, Xin; Fan, Ruihua; Chen, Yiming; Zhai, Hui; Zhang, Pengfei

2017-11-17

The Sachdev-Ye-Kitaev (SYK) model is a concrete solvable model to study non-Fermi liquid properties, holographic duality, and maximally chaotic behavior. In this work, we consider a generalization of the SYK model that contains two SYK models with a different number of Majorana modes coupled by quadratic terms. This model is also solvable, and the solution shows a zero-temperature quantum phase transition between two non-Fermi liquid chaotic phases. This phase transition is driven by tuning the ratio of two mode numbers, and a nonchaotic Fermi liquid sits at the critical point with an equal number of modes. At a finite temperature, the Fermi liquid phase expands to a finite regime. More intriguingly, a different non-Fermi liquid phase emerges at a finite temperature. We characterize the phase diagram in terms of the spectral function, the Lyapunov exponent, and the entropy. Our results illustrate a concrete example of the quantum phase transition and critical behavior between two non-Fermi liquid phases.

Gas-liquid chromatography with a volatile "stationary" liquid phase.

PubMed

Wells, P S; Zhou, S; Parcher, J F

2002-05-01

A unique type of gas-liquid chromatography is described in which both mobile and "stationary" phases are composed of synthetic mixtures of helium and carbon dioxide. At temperatures below the critical point of the binary mixture and pressures above the vapor pressure of pure liquid carbon dioxide, helium and carbon dioxide can form two immiscible phases over extended composition ranges. A binary vapor phase enriched in helium can act as the mobile phase for chromatographic separations, whereas a CO2-rich liquid in equilibrium with the vapor phase, but condensed on the column wall, can act as a pseudostationary phase. Several examples of chromatographic separations obtained in "empty" capillary columns with no ordinary stationary liquid phase illustrate the range of conditions that produce such separations. In addition, several experiments are reported that confirm the proposed two-phase hypothesis. The possible consequences of the observed chromatographic phenomenon in the field of supercritical fluid chromatography with helium headspace carbon dioxide are discussed.

Critical point analysis of phase envelope diagram

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

Soetikno, Darmadi; Siagian, Ucok W. R.; Kusdiantara, Rudy, E-mail: rkusdiantara@s.itb.ac.id

2014-03-24

Phase diagram or phase envelope is a relation between temperature and pressure that shows the condition of equilibria between the different phases of chemical compounds, mixture of compounds, and solutions. Phase diagram is an important issue in chemical thermodynamics and hydrocarbon reservoir. It is very useful for process simulation, hydrocarbon reactor design, and petroleum engineering studies. It is constructed from the bubble line, dew line, and critical point. Bubble line and dew line are composed of bubble points and dew points, respectively. Bubble point is the first point at which the gas is formed when a liquid is heated. Meanwhile,more » dew point is the first point where the liquid is formed when the gas is cooled. Critical point is the point where all of the properties of gases and liquids are equal, such as temperature, pressure, amount of substance, and others. Critical point is very useful in fuel processing and dissolution of certain chemicals. Here in this paper, we will show the critical point analytically. Then, it will be compared with numerical calculations of Peng-Robinson equation by using Newton-Raphson method. As case studies, several hydrocarbon mixtures are simulated using by Matlab.« less

Molecular Modeling of Three Phase Contact for Static and Dynamic Contact Angle Phenomena

NASA Astrophysics Data System (ADS)

Malani, Ateeque; Amat, Miguel; Raghavanpillai, Anilkumar; Wysong, Ernest; Rutledge, Gregory

2012-02-01

Interfacial phenomena arise in a number of industrially important situations, such as repellency of liquids on surfaces, condensation, etc. In designing materials for such applications, the key component is their wetting behavior, which is characterized by three-phase static and dynamic contact angle phenomena. Molecular modeling has the potential to provide basic insight into the detailed picture of the three-phase contact line resolved on the sub-nanometer scale which is essential for the success of these materials. We have proposed a computational strategy to study three-phase contact phenomena, where buoyancy of a solid rod or particle is studied in a planar liquid film. The contact angle is readily evaluated by measuring the position of solid and liquid interfaces. As proof of concept, the methodology has been validated extensively using a simple Lennard-Jones (LJ) fluid in contact with an LJ surface. In the dynamic contact angle analysis, the evolution of contact angle as a function of force applied to the rod or particle is characterized by the pinning and slipping of the three phase contact line. Ultimately, complete wetting or de-wetting is observed, allowing molecular level characterization of the contact angle hysteresis.

Determination of metal ions in tea samples using task-specific ionic liquid-based ultrasound-assisted dispersive liquid-liquid microextraction coupled to liquid chromatography with ultraviolet detection.

PubMed

Werner, Justyna

2016-04-01

Task-specific ionic liquid-based ultrasound-assisted dispersive liquid-liquid microextraction was used for the preconcentration of cadmium(II), cobalt(II), and lead(II) ions in tea samples, which were subsequently analyzed by liquid chromatography with UV detection. The proposed method of preconcentration is free of volatile organic compounds, which are often used as extractants and dispersing solvents in classic techniques of microextraction. A task-specific ionic liquid trioctylmethylammonium thiosalicylate was used as an extractant and a chelating agent. Ultrasound was used to disperse the ionic liquid. After microextraction, the phases were separated by centrifugation, and the ionic liquid phase was solubilized in methanol and directly injected into the liquid chromatograph. Selected microextraction parameters, such as the volume of ionic liquid, the pH of the sample, the duration of ultrasound treatment, the speed and time of centrifugation, and the effect of ionic strength, were optimized. Under optimal conditions an enrichment factor of 200 was obtained for each analyte. The limits of detection were 0.002 mg/kg for Cd(II), 0.009 mg/kg for Co(II), and 0.013 mg/kg for Pb(II). The accuracy of the proposed method was evaluated by an analysis of the Certified Reference Materials (INCT-TL-1, INCT-MPH-2) with the recovery values in the range of 90-104%. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hydrogen, lithium, and lithium hydride production

DOEpatents

Brown, Sam W.; Spencer, Larry S.; Phillips, Michael R.; Powell, G. Louis; Campbell, Peggy J.

2017-06-20

A method is provided for extracting hydrogen from lithium hydride. The method includes (a) heating lithium hydride to form liquid-phase lithium hydride; (b) extracting hydrogen from the liquid-phase lithium hydride, leaving residual liquid-phase lithium metal; (c) hydriding the residual liquid-phase lithium metal to form refined lithium hydride; and repeating steps (a) and (b) on the refined lithium hydride.

Study of two-phase flows in reduced gravity

NASA Astrophysics Data System (ADS)

Roy, Tirthankar

Study of gas-liquid two-phase flows under reduced gravity conditions is extremely important. One of the major applications of gas-liquid two-phase flows under reduced gravity conditions is in the design of active thermal control systems for future space applications. Previous space crafts were characterized by low heat generation within the spacecraft which needed to be redistributed within the craft or rejected to space. This task could easily have been accomplished by pumped single-phase loops or passive systems such as heat pipes and so on. However with increase in heat generation within the space craft as predicted for future missions, pumped boiling two-phase flows are being considered. This is because of higher heat transfer co-efficients associated with boiling heat transfer among other advantages. Two-phase flows under reduced gravity conditions also find important applications in space propulsion as in space nuclear power reactors as well as in many other life support systems of space crafts. Two-fluid model along with Interfacial Area Transport Equation (IATE) is a useful tool available to predict the behavior of gas-liquid two-phase flows under reduced gravity conditions. It should be noted that considerable differences exist between two-phase flows under reduced and normal gravity conditions especially for low inertia flows. This is because due to suppression of the gravity field the gas-liquid two-phase flows take a considerable time to develop under reduced gravity conditions as compared to normal gravity conditions. Hence other common methods of analysis applicable for fully developed gas-liquid two-phase flows under normal gravity conditions, like flow regimes and flow regime transition criteria, will not be applicable to gas-liquid two-phase flows under reduced gravity conditions. However the two-fluid model and the IATE need to be evaluated first against detailed experimental data obtained under reduced gravity conditions. Although lot of studies have been done in the past to understand the global structure of gas-liquid two-phase flows under reduced gravity conditions, using experimental setups aboard drop towers or aircrafts flying parabolic flights, detailed data on local structure of such two-phase flows are extremely rare. Hence experiments were carried out in a 304 mm inner diameter (ID) test facility on earth. Keeping in mind the detailed experimental data base that needs to be generated to evaluate two-fluid model along with IATE, ground based simulations provide the only economic path. Here the reduced gravity condition is simulated using two-liquids of similar densities (water and Therminol 59 RTM in the present case). Only adiabatic two-phase flows were concentrated on at this initial stage. Such a large diameter test section was chosen to study the development of drops to their full extent (it is to be noted that under reduced gravity conditions the stable bubble size in gas-liquid two-phase flows is much larger than that at normal gravity conditions). Twelve flow conditions were chosen around predicted bubbly flow to cap-bubbly flow transition region. Detailed local data was obtained at ten radial locations for each of three axial locations using state-of-the art multi-sensor conductivity probes. The results are presented and discussed. Also one-group as well as two-group, steady state, one-dimensional IATE was evaluated against data obtained here and by other researchers, and the results presented and discussed.

Understanding rapid changes in phase partitioning between cloud liquid and ice in an Arctic stratiform mixed-phase cloud

NASA Astrophysics Data System (ADS)

Kalesse, Heike; de Boer, Gijs; Solomon, Amy; Oue, Mariko; Ahlgrimm, Maike; Zhang, Damao; Shupe, Matthew; Luke, Edward; Protat, Alain

2016-04-01

In the Arctic, a region particularly sensitive to climate change, mixed-phase clouds occur as persistent single or multiple stratiform layers. For many climate models, the correct partitioning of hydrometeor phase (liquid vs. ice) remains a challenge. However, this phase partitioning plays an important role for precipitation processes and the radiation budget. To better understand the partitioning of phase in Arctic clouds, observations using a combination of surface-based remote sensors are useful. In this study, the focus is on a persistent low-level single-layer stratiform Arctic mixed-phase cloud observed during March 11-12, 2013 at the US Department of Energy's (DOE) Atmospheric Radiation Measurement (ARM) North Slope of Alaska (NSA) permanent site in Barrow, Alaska. This case is of particular interest due to two significant shifts in observed precipitation intensity over a 36 hour period. For the first 12 hours of this case, the observed liquid portion of the cloud cover featured a stable cloud top height with a gradually descending liquid cloud base and continuous ice precipitation. Then the ice precipitation intensity significantly decreased. A second decrease in ice precipitation intensity was observed a few hours later coinciding with the advection of a cirrus over the site. Through analysis of the data collected by extensive ground-based remote-sensing and in-situ observing systems as well as Nested Weather Research and Forecasting (WRF) simulations and ECMWF radiation scheme simulations, we try to shed light on the processes responsible for these rapid changes in precipitation rates. A variety of parameters such as the evolution of the internal dynamics and microphysics of the low-level mixed-phase cloud and the influence of the cirrus cloud are evaluated.

[Determination of seven phenoxyacid herbicides in environmental water by high performance liquid chromatography coupled with three phase hollow fiber liquid phase microextraction].

PubMed

Peng, Xiaojun; Pang, Jinshan; Deng, Aihua

2011-12-01

A novel method for the simultaneous determination of seven phenoxyacid herbicides such as dicamba, fluroxypyr, 4-chlorophenoxyacetic acid (4-CPA), 2-methyl-4-chlorophenoxyacetic acid (MCPA), 2, 4-dichlorophenoxyacetic acid (2,4-D), 2,4-dichlorophenoxybutyric acid (2,4-DB) and 4-(2-methyl-4-chlorophenoxy) butyric acid (MCPB) in environmental water by three phase hollow fiber liquid phase microextraction (HF-LPME) coupled with high performance liquid chromatography (HPLC) was developed. In order to optimize the experimental conditions, the orthogonal test has been used. The effects of extraction solvent, pH of the donor phase and acceptor phase, extraction time, stirring speed and salt concentration on the detection were investigated. The optimal experimental conditions were as follows: octanol as organic solvent, pH 3 of donor phase, pH 12 of acceptor phase, extraction time of 30 min, stirring speed of 400 r/min. The results showed that the proposed method provided a wide linear range for 7 phenoxyacid herbicides with correlation coefficients of 0.995 3 - 0.998 8. The detection limits ranged from 0.2 to 1.0 microg/L. The enrichment factors were in the range of 76.7 - 121. The recoveries were in the range of 68% - 104% and the relative standard deviations (RSDs) were less than 8.1% for the environmental water samples. The method has the advantages of sensitivity, simplicity, fastness and the use of very small amounts of organic solvent. The method can meet the requirements of the determination of trace phenoxyacid herbicides in the environmental water samples, and the study provided a useful method for the analysis of trace substances in water samples.

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

PubMed

Matsuyama, Akihiko

2009-11-28

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

Study of gas-liquid flow in model porous media for heterogeneous catalysis

NASA Astrophysics Data System (ADS)

Francois, Marie; Bodiguel, Hugues; Guillot, Pierre; Laboratory of the Future Team

2015-11-01

Heterogeneous catalysis of chemical reactions involving a gas and a liquid phase is usually achieved in fixed bed reactors. Four hydrodynamic regimes have been observed. They depend on the total flow rate and the ratio between liquid and gas flow rate. Flow properties in these regimes influence transfer rates. Rather few attempts to access local characterization have been proposed yet, though these seem to be necessary to better describe the physical mechanisms involved. In this work, we propose to mimic slices of reactor by using two-dimensional porous media. We have developed a two-dimensional system that is transparent to allow the direct observation of the flow and the phase distribution. While varying the total flow rate and the gas/liquid flow rate ratio, we observe two hydrodynamic regimes: at low flow rate, the gaseous phase is continuous (trickle flow), while it is discontinuous at higher flow rate (pulsed flow). Thanks to some image analysis techniques, we are able to quantify the local apparent liquid saturation in the system. Its fluctuations in time are characteristic of the transition between the two regimes: at low liquid flow rates, they are negligible since the liquid/gas interface is fixed, whereas at higher flow rates we observe an alternation between liquid and gas. This transition between trickle to pulsed flow is in relative good agreement with the existing state of art. However, we report in the pulsed regime important flow heterogeneities at the scale of a few pores. These heterogeneities are likely to have a strong influence on mass transfers. We acknowledge the support of Solvay.

Liquid-Crystal Point-Diffraction Interferometer for Wave-Front Measurements

NASA Technical Reports Server (NTRS)

Mercer, Carolyn R.; Creath, Katherine

1996-01-01

A new instrument, the liquid-crystal point-diffraction interferometer (LCPDI), is developed for the measurement of phase objects. This instrument maintains the compact, robust design of Linnik's point-diffraction interferometer and adds to it a phase-stepping capability for quantitative interferogram analysis. The result is a compact, simple to align, environmentally insensitive interferometer capable of accurately measuring optical wave fronts with very high data density and with automated data reduction. We describe the theory and design of the LCPDI. A focus shift was measured with the LCPDI, and the results are compared with theoretical results,

Nonclassical effects in liquid-phase nuclear magnetic resonance spectra of 9-methyltriptycene derivatives

NASA Astrophysics Data System (ADS)

Czerski, I.; Bernatowicz, P.; Jaźwiński, J.; Szymański, S.

2003-04-01

The dynamics of strongly hindered methyl groups in 9-methyltriptycene derivatives, monitored by liquid-phase nuclear magnetic resonance spectra, were investigated using an iterative, least-squares method of line shape analysis. For two of the compounds, apart from nonclassical effects in the stochastic dynamics, anomalously strong dependence on temperature (ca. 0.05 and 0.08 Hz/K) of the J coupling between the methyl protons was observed. The latter effect was attributed to the occurrence of coherent quantum tunneling of the methyl rotor. For methyl group, this would be the first observation of coherent tunneling above cryogenic temperatures.

Liquid-liquid phase transformations and the shape of the melting curve.

PubMed

Makov, G; Yahel, E

2011-05-28

The phase diagram of elemental liquids has been found to be surprisingly rich, including variations in the melting curve and transitions in the liquid phase. The effect of these transitions in the liquid state on the shape of the melting curve is analyzed. First-order phase transitions intersecting the melting curve imply piecewise continuous melting curves, with solid-solid transitions generating upward kinks or minima and liquid-liquid transitions generating downward kinks or maxima. For liquid-liquid phase transitions proposed for carbon, phosphorous selenium, and possibly nitrogen, we find that the melting curve exhibits a kink. Continuous transitions imply smooth extrema in the melting curve, the curvature of which is described by an exact thermodynamic relation. This expression indicates that a minimum in the melting curve requires the solid compressibility to be greater than that of the liquid, a very unusual situation. This relation is employed to predict the loci of smooth maxima at negative pressures for liquids with anomalous melting curves. The relation between the location of the melting curve maximum and the two-state model of continuous liquid-liquid transitions is discussed and illustrated by the case of tellurium. © 2011 American Institute of Physics

Fluid inclusions in minerals from the geothermal fields of Tuscany, Italy

USGS Publications Warehouse

Belkin, H.; de Vivo, B.; Gianelli, G.; Lattanzi, P.

1985-01-01

A reconnaissance study on fluid inclusions from the geothermal fields of Tuscany indicates that the hydrothermal minerals were formed by fluids which were, at least in part, boiling. Four types of aqueous inclusions were recognized: (A) two-phase (liquid + vapor) liquid rich, (B) two-phase (vapor + liquid) vapor rich, (C) polyphase hypersaline liquid rich and (D) three phase-H2O liquid + CO2 liquid + CO2-rich vapor. Freezing and heating microthermometric determinations are reported for 230 inclusions from samples from six wells. It is suggested that boiling of an originally homogeneous, moderately saline, CO2-bearing liquid phase produced a residual hypersaline brine and a CO2-rich vapor phase. There are indications of a temperature decrease in the geothermal field of Larderello, especially in its peripheral zones. ?? 1985.

Methylxanthines: properties and determination in various objects

NASA Astrophysics Data System (ADS)

Andreeva, Elena Yu; Dmitrienko, Stanislava G.; Zolotov, Yurii A.

2012-05-01

Published data on the properties and determination of caffeine, theophylline, theobromine and some other methylxanthines in various objects are surveyed and described systematically. Different sample preparation procedures such as liquid extraction from solid matrices and liquid-liquid, supercritical fluid and solid-phase extraction are compared. The key methods of analysis including chromatography, electrophoresis, spectrometry and electrochemical methods are discussed. Examples of methylxanthine determination in plants, food products, energy beverages, pharmaceuticals, biological fluids and natural and waste waters are given. The bibliography includes 393 references.

Dirac points, spinons and spin liquid in twisted bilayer graphene

NASA Astrophysics Data System (ADS)

Irkhin, V. Yu.; Skryabin, Yu. N.

2018-05-01

Twisted bilayer graphene is an excellent example of highly correlated system demonstrating a nearly flat electron band, the Mott transition and probably a spin liquid state. Besides the one-electron picture, analysis of Dirac points is performed in terms of spinon Fermi surface in the limit of strong correlations. Application of gauge field theory to describe deconfined spin liquid phase is treated. Topological quantum transitions, including those from small to large Fermi surface in the presence of van Hove singularities, are discussed.

Quantitative analysis of phylloquinone (vitamin K1) in soy bean oils by high-performance liquid chromatography.

PubMed

Zonta, F; Stancher, B

1985-07-19

A high-performance liquid chromatographic method for determining phylloquinone (vitamin K1) in soy bean oils is described. Resolution of vitamin K1 from interfering peaks of the matrix was obtained after enzymatic digestion, extraction and liquid-solid chromatography on alumina. An isocratic reversed-phase chromatography with UV detection was used in the final stage. The quantitation was carried out by the standard addition method, and the recovery of the whole procedure was 88.2%.

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.

Formation of liquid crystalline phases in aqueous suspensions of platelet-like tripalmitin nanoparticles

NASA Astrophysics Data System (ADS)

Schmiele, Martin; Gehrer, Simone; Westermann, Martin; Steiniger, Frank; Unruh, Tobias

2014-06-01

Suspensions of platelet-like shaped tripalmitin nanocrystals stabilized by the pure lecithin DLPC and the lecithin blend S100, respectively, have been studied by small-angle x-ray scattering (SAXS) and optical observation of their birefringence at different tripalmitin (PPP) concentrations φPPP. It could be demonstrated that the platelets of these potential drug delivery systems start to form a liquid crystalline phase already at pharmaceutically relevant concentrations φPPP of less than 10 wt. %. The details of this liquid crystalline phase are described here for the first time. As in a previous study [A. Illing et al., Pharm. Res. 21, 592 (2004)] some platelets are found to self-assemble into lamellar stacks above a critical tripalmitin concentration \\varphi _{PPP}^{st} of 4 wt. %. In this study another critical concentration \\varphi _{PPP}^{lc}≈ 7 wt. % for DLPC and \\varphi _{PPP}^{lc}≈ 9 wt. % for S100 stabilized dispersions, respectively, has been observed. \\varphi _{PPP}^{lc} describes the transition from a phase of randomly oriented stacked lamellae and remaining non-assembled individual platelets to a phase in which the stacks and non-assembled platelets exhibit an overall preferred orientation. A careful analysis of the experimental data indicates that for concentrations above \\varphi _{PPP}^{lc} the stacked lamellae start to coalesce to rather small liquid crystalline domains of nematically ordered stacks. These liquid crystalline domains can be individually very differently oriented but possess an overall preferred orientation over macroscopic length scales which becomes successively more expressed when further increasing φPPP. The lower critical concentration for the formation of liquid crystalline domains of the DLPC-stabilized suspension compared to \\varphi _{PPP}^{lc} of the S100-stabilized suspension can be explained by a larger aspect ratio of the corresponding tripalmitin platelets. A geometrical model based on the excluded volumes of individual platelets and stacked lamellae has been developed and successfully applied to reproduce the critical volume fractions for both, the onset of stack formation and the appearance of the liquid crystalline phase.

Orientation of liquid crystalline blue phases on unidirectionally orienting surfaces

NASA Astrophysics Data System (ADS)

Takahashi, Misaki; Ohkawa, Takuma; Yoshida, Hiroyuki; Fukuda, Jun-ichi; Kikuchi, Hirostugu; Ozaki, Masanori

2018-03-01

Liquid crystalline cholesteric blue phases (BPs) continue to attract interest due to their fast response times and quasi-polarization-independent phase modulation capabilities. Various approaches have recently been proposed to control the crystal orientation of BPs on substrates; however, their basic orientation properties on standard, unidirectionally orienting alignment layers have not been investigated in detail. Through analysis of the azimuthal orientation of Kossel diagrams, we study the 3D crystal orientation of a BP material—with a phase sequence of cholesteric, BP I, and BP II—on unidirectionally orienting surfaces prepared using two methods: rubbing and photoalignment. BP II grown from the isotropic phase is sensitive to surface conditions, with different crystal planes orienting on the two substrates. On the other hand, strong thermal hysteresis is observed in BPs grown through a different liquid crystal phase, implying that the preceding structure determines the orientation. More specifically, the BP II-I transition is accompanied by a rotation of the crystal such that the crystal direction defined by certain low-value Miller indices transform into different directions, and within the allowed rotations, different azimuthal configurations are obtained in the same cell depending on the thermal process. Our findings demonstrate that, for the alignment control of BPs, the thermal process is as important as the properties of the alignment layer.

Modelling Phase Transition Phenomena in Fluids

DTIC Science & Technology

2015-07-01

Sublimation line r @@I Triple point ? Vapourisation liner @@I Critical point -Fusion line Solid Liquid Gas Figure 1: Schematic of a phase diagram means that the...velocity field can be set zero, and only the balance of energy constitutes the Stefan model. In contrast to this the liquid - gas phase transitions...defined by requiring that the phase-transition line is crossed in a direction from solid to liquid or from liquid to gas (vapour) phases. The term T∗ δs is

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

Development of a dispersive liquid-liquid microextraction method using a lighter-than-water ionic liquid for the analysis of polycyclic aromatic hydrocarbons in water.

PubMed

Medina, Giselle S; Reta, Mario

2016-11-01

A dispersive liquid-liquid microextraction method using a lighter-than-water phosphonium-based ionic liquid for the extraction of 16 polycyclic aromatic hydrocarbons from water samples has been developed. The extracted compounds were analyzed by liquid chromatography coupled to fluorescence/diode array detectors. The effects of several experimental parameters on the extraction efficiency, such as type and volume of ionic liquid and disperser solvent, type and concentration of salt in the aqueous phase and extraction time, were investigated and optimized. Three phosphonium-based ionic liquids were assayed, obtaining larger extraction efficiencies when trihexyl-(tetradecyl)phosphonium bromide was used. The optimized methodology requires a few microliters of a lighter-than-water phosphonium-based ionic liquid, which allows an easy separation of the extraction solvent phase. The obtained limits of detection were between 0.02 and 0.56 μg/L, enrichment factors between 109 and 228, recoveries between 60 and 108%, trueness between 0.4 and 9.9% and reproducibility values between 3 and 12% were obtained. These figures of merit combined with the simplicity, rapidity and low cost of the analytical methodology indicate that this is a viable and convenient alternative to the methods reported in the literature. The developed method was used to analyze polycyclic aromatic hydrocarbons in river water samples. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

IN SITU SOLID-PHASE EXTRACTION AND ANALYSIS OF ULTRA-TRACE SYNTHETIC MUSKS IN MUNICIPAL SEWAGE EFFLUENT USING GAS CHROMATOGRAPHY-MASS SPECTROMETRY, FULL-SCAN MODE

EPA Science Inventory

Fragrance materials, such as synthetic musks in aqueous samples, are normally analyzed by GC/MS in the selected ion monitoring (SIM) mode to provide maximum sensitivity after liquid-liquid extraction of 1-L samples. A 1-L sample, however, usually provides too little ana...

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.

ON-SITE SOLID-PHASE EXTRACTION AND LABORATORY ANALYSIS OF ULTRA-TRACE SYNTHETIC MUSKS IN MUNICIPAL SEWAGE EFFLUENT USING GAS CHROMATOGRAPHY-MASS SPECTROMETRY IN THE FULL-SCAN MODE

EPA Science Inventory

Fragrance materials such as synthetic musks in aqueous samples, are normally determined by gas chromatography/mass spectrometry in the selected ion monitoring (SIM) mode to provide maximum sensitivity after liquid-liquid extraction of I -L samples. Full-scan mass spectra are requ...

Poly(ionic liquids)-coated stainless-steel wires packed into a polyether ether ketone tube for in-tube solid-phase microextraction.

PubMed

Feng, Juanjuan; Wang, Xiuqin; Tian, Yu; Luo, Chuannan; Sun, Min

2017-12-01

An in-tube solid-phase microextraction device was developed by packing poly(ionic liquids)-coated stainless-steel wires into a polyether ether ketone tube. An anion-exchange process was performed to enhance the extraction performance. Surface properties of poly(ionic liquids)-coated stainless-steel wires were characterized by scanning electron microscopy and energy dispersive X-ray spectrometry. The extraction device was connected to high-performance liquid chromatography equipment to build an online enrichment and analysis system. Ten polycyclic aromatic hydrocarbons were used as model analytes, and important conditions including extraction time and desorption time were optimized. The enrichment factors from 268 to 2497, linear range of 0.03-20 μg/L, detection limits of 0.010-0.020 μg/L, extraction and preparation repeatability with relative standard deviation less than 1.8 and 19%, respectively were given by the established online analysis method. It has been used to detect polycyclic aromatic hydrocarbons in environmental samples, with the relative recovery (5, 10 μg/L) in the range of 85.1-118.9%. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Espresso coffee foam delays cooling of the liquid phase.

PubMed

Arii, Yasuhiro; Nishizawa, Kaho

2017-04-01

Espresso coffee foam, called crema, is known to be a marker of the quality of espresso coffee extraction. However, the role of foam in coffee temperature has not been quantitatively clarified. In this study, we used an automatic machine for espresso coffee extraction. We evaluated whether the foam prepared using the machine was suitable for foam analysis. After extraction, the percentage and consistency of the foam were measured using various techniques, and changes in the foam volume were tracked over time. Our extraction method, therefore, allowed consistent preparation of high-quality foam. We also quantitatively determined that the foam phase slowed cooling of the liquid phase after extraction. High-quality foam plays an important role in delaying the cooling of espresso coffee.

Exfoliation in ecstasy: liquid crystal formation and concentration-dependent debundling observed for single-wall nanotubes dispersed in the liquid drug γ-butyrolactone

NASA Astrophysics Data System (ADS)

Bergin, Shane D.; Nicolosi, Valeria; Giordani, Silvia; de Gromard, Antoine; Carpenter, Leslie; Blau, Werner J.; Coleman, Jonathan N.

2007-11-01

Large-scale debundling of single-walled nanotubes has been demonstrated by dilution of nanotube dispersions in the solvent γ-butyrolactone. This liquid, sometimes referred to as 'liquid ecstasy', is well known for its narcotic properties. At high concentrations the dispersions form an anisotropic, liquid crystalline phase which can be removed by mild centrifugation. At lower concentrations an isotropic phase is observed with a biphasic region at intermediate concentrations. By measuring the absorbance before and after centrifugation, as a function of concentration, the relative anisotropic and isotropic nanotube concentrations can be monitored. The upper limit of the pure isotropic phase was CNT~0.004 mg ml-1, suggesting that this can be considered the nanotube dispersion limit in γ-butyrolactone. After centrifugation, the dispersions are stable against sedimentation and further aggregation for a period of 8 weeks at least. Atomic-force-microscopy studies on films deposited from the isotropic phase reveal that the bundle diameter distribution decreases dramatically as concentration is decreased. Detailed data analysis suggests the presence of an equilibrium bundle number density. A population of individual nanotubes is always observed which increases with decreasing concentration until almost 40% of all dispersed objects are individual nanotubes at a concentration of 6 × 10-4 mg ml-1. The number density of individual nanotubes peaks at a concentration of ~6 × 10-3 mg ml-1 where almost 10% of the nanotubes by mass are individualized.

Stabilizing liquid drops of arbitrary shape by the interfacial jamming of nanoparticles

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

Russell, Thomas P.; Cui, Mengmeng; Emrick, Todd

A stabilized assembly including a first liquid phase of non-spherical droplets in a second liquid phase, wherein the second liquid phase is immiscible with the first phase, and nanoparticle surfactants assembled at an interface of the non-spherical droplets and the second phase is disclosed. The nanoparticle surfactants include nanoparticles and end-functionalized polymers that can interact through ligand type interactions, and the first phase is stabilized by a disordered, jammed layer of nanoparticle surfactants. A method of preparing a stabilized assembly is also disclosed.

An Isotopic Dilution Experiment Using Liquid Scintillation: A Simple Two-System, Two-Phase Analysis.

ERIC Educational Resources Information Center

Moehs, Peter J.; Levine, Samuel

1982-01-01

A simple isotonic, dilution analysis whose principles apply to methods of more complex radioanalyses is described. Suitable for clinical and instrumental analysis chemistry students, experimental manipulations are kept to a minimum involving only aqueous extraction before counting. Background information, procedures, and results are discussed.…

How ionic species structure influences phase structure and transitions from protic ionic liquids to liquid crystals to crystals.

PubMed

Greaves, Tamar L; Broomhall, Hayden; Weerawardena, Asoka; Osborne, Dale A; Canonge, Bastien A; Drummond, Calum J

2017-12-14

The phase behaviour of n-alkylammonium (C6 to C16) nitrates and formates has been characterised using synchrotron small angle and wide angle X-ray scattering (SAXS/WAXS), differential scanning calorimetry (DSC), cross polarised optical microscopy (CPOM) and Fourier transform infrared spectroscopy (FTIR). The protic salts may exist as crystalline, liquid crystalline or ionic liquid materials depending on the alkyl chain length and temperature. n-Alkylammonium nitrates with n ≥ 6 form thermotropic liquid crystalline (LC) lamellar phases, whereas n ≥ 8 was required for the formate series to form this LC phase. The protic ionic liquid phase showed an intermediate length scale nanostructure resulting from the segregation of the polar and nonpolar components of the ionic liquid. This segregation was enhanced for longer n-alkyl chains, with a corresponding increase in the correlation length scale. The crystalline and liquid crystalline phases were both lamellar. Phase transition temperatures, lamellar d-spacings, and liquid correlation lengths for the n-alkylammonium nitrates and formates were compared with those for n-alkylammonium chlorides and n-alkylamines. Plateau regions in the liquid crystalline to liquid phase transition temperatures as a function of n for the n-alkylammonium nitrates and formates are consistent with hydrogen-bonding and cation-anion interactions between the ionic species dominating alkyl chain-chain van der Waals interactions, with the exception of the mid chained hexyl- and heptylammonium formates. The d-spacings of the lamellar phases for both the n-alkylammonium nitrates and formates were consistent with an increase in chain-chain layer interdigitation within the bilayer-based lamellae with increasing alkyl chain length, and they were comparable to the n-alkylammonium chlorides.

Gallium-rich Pd-Ga phases as supported liquid metal catalysts

NASA Astrophysics Data System (ADS)

Taccardi, N.; Grabau, M.; Debuschewitz, J.; Distaso, M.; Brandl, M.; Hock, R.; Maier, F.; Papp, C.; Erhard, J.; Neiss, C.; Peukert, W.; Görling, A.; Steinrück, H.-P.; Wasserscheid, P.

2017-09-01

A strategy to develop improved catalysts is to create systems that merge the advantages of heterogeneous and molecular catalysis. One such system involves supported liquid-phase catalysts, which feature a molecularly defined, catalytically active liquid film/droplet layer adsorbed on a porous solid support. In the past decade, this concept has also been extended to supported ionic liquid-phase catalysts. Here we develop this idea further and describe supported catalytically active liquid metal solutions (SCALMS). We report a liquid mixture of gallium and palladium deposited on porous glass that forms an active catalyst for alkane dehydrogenation that is resistant to coke formation and is thus highly stable. X-ray diffraction and X-ray photoelectron spectroscopy, supported by theoretical calculations, confirm the liquid state of the catalytic phase under the reaction conditions. Unlike traditional heterogeneous catalysts, the supported liquid metal reported here is highly dynamic and catalysis does not proceed at the surface of the metal nanoparticles, but presumably at homogeneously distributed metal atoms at the surface of a liquid metallic phase.

Evaluation of the pathways of tropospheric nitrophenol formation from benzene and phenol using a multiphase model

NASA Astrophysics Data System (ADS)

Harrison, M. A. J.; Heal, M. R.; Cape, J. N.

2005-07-01

Phenols are a major class of volatile organic compounds (VOC) whose reaction within, and partitioning between, the gas and liquid phases affects their lifetime within the atmosphere, the local oxidising capacity, and the extent of production of nitrophenols, which are toxic chemicals. In this work, a zero-dimension box model was constructed to quantify the relative importance of different nitration pathways, and partitioning into the liquid phase, of mono-aromatic compounds in order to help elucidate the formation pathways of 2- and 4-nitrophenol in the troposphere. The liquid phase contributed significantly to the production of nitrophenols for liquid water content (Lc) values exceeding 3x10-9, and for a range of assumed liquid droplet diameter, even though the resultant equilibrium partitioning to the liquid phase was much lower. For example, in a "typical" model scenario, with Lc=3x10-7, 58% of nitrophenol production occurred in the liquid phase but only 2% of nitrophenol remained there, i.e. a significant proportion of nitrophenol observed in the gas phase may actually be produced via the liquid phase. The importance of the liquid phase was enhanced at lower temperatures, by a factor ~1.5-2 at 278K c.f. 298K. The model showed that nitrophenol production was particularly sensitive to the values of the rate coefficients for the liquid phase reactions between phenol and OH or NO3 reactions, but insensitive to the rate coefficient for the reaction between benzene and OH, thus identifying where further experimental data are required.

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.

Linear Stability Analysis of an Acoustically Vaporized Droplet

NASA Astrophysics Data System (ADS)

Siddiqui, Junaid; Qamar, Adnan; Samtaney, Ravi

2015-11-01

Acoustic droplet vaporization (ADV) is a phase transition phenomena of a superheat liquid (Dodecafluoropentane, C5F12) droplet to a gaseous bubble, instigated by a high-intensity acoustic pulse. This approach was first studied in imaging applications, and applicable in several therapeutic areas such as gas embolotherapy, thrombus dissolution, and drug delivery. High-speed imaging and theoretical modeling of ADV has elucidated several physical aspects, ranging from bubble nucleation to its subsequent growth. Surface instabilities are known to exist and considered responsible for evolving bubble shapes (non-spherical growth, bubble splitting and bubble droplet encapsulation). We present a linear stability analysis of the dynamically evolving interfaces of an acoustically vaporized micro-droplet (liquid A) in an infinite pool of a second liquid (liquid B). We propose a thermal ADV model for the base state. The linear analysis utilizes spherical harmonics (Ynm, of degree m and order n) and under various physical assumptions results in a time-dependent ODE of the perturbed interface amplitudes (one at the vapor/liquid A interface and the other at the liquid A/liquid B interface). The perturbation amplitudes are found to grow exponentially and do not depend on m. Supported by KAUST Baseline Research Funds.

Jet-mixing of initially-stratified liquid-liquid pipe flows: experiments and numerical simulations

NASA Astrophysics Data System (ADS)

Wright, Stuart; Ibarra-Hernandes, Roberto; Xie, Zhihua; Markides, Christos; Matar, Omar

2016-11-01

Low pipeline velocities lead to stratification and so-called 'phase slip' in horizontal liquid-liquid flows due to differences in liquid densities and viscosities. Stratified flows have no suitable single point for sampling, from which average phase properties (e.g. fractions) can be established. Inline mixing, achieved by static mixers or jets in cross-flow (JICF), is often used to overcome liquid-liquid stratification by establishing unstable two-phase dispersions for sampling. Achieving dispersions in liquid-liquid pipeline flows using JICF is the subject of this experimental and modelling work. The experimental facility involves a matched refractive index liquid-liquid-solid system, featuring an ETFE test section, and experimental liquids which are silicone oil and a 51-wt% glycerol solution. The matching then allows the dispersed fluid phase fractions and velocity fields to be established through advanced optical techniques, namely PLIF (for phase) and PTV or PIV (for velocity fields). CFD codes using the volume of a fluid (VOF) method are then used to demonstrate JICF breakup and dispersion in stratified pipeline flows. A number of simple jet configurations are described and their dispersion effectiveness is compared with the experimental results. Funding from Cameron for Ph.D. studentship (SW) gratefully acknowledged.

Comprehensive modeling of a liquid rocket combustion chamber

NASA Technical Reports Server (NTRS)

Liang, P.-Y.; Fisher, S.; Chang, Y. M.

1985-01-01

An analytical model for the simulation of detailed three-phase combustion flows inside a liquid rocket combustion chamber is presented. The three phases involved are: a multispecies gaseous phase, an incompressible liquid phase, and a particulate droplet phase. The gas and liquid phases are continuum described in an Eulerian fashion. A two-phase solution capability for these continuum media is obtained through a marriage of the Implicit Continuous Eulerian (ICE) technique and the fractional Volume of Fluid (VOF) free surface description method. On the other hand, the particulate phase is given a discrete treatment and described in a Lagrangian fashion. All three phases are hence treated rigorously. Semi-empirical physical models are used to describe all interphase coupling terms as well as the chemistry among gaseous components. Sample calculations using the model are given. The results show promising application to truly comprehensive modeling of complex liquid-fueled engine systems.

Characterization of Gas Chromatographic Liquid Phases Using McReynolds Constants. An Experiment for Instrumental Analysis Laboratory.

ERIC Educational Resources Information Center

Erskine, Steven R.; And Others

1986-01-01

Describes a laboratory experiment that is designed to aid in the understanding of the fundamental process involved in gas chromatographic separations. Introduces the Kovats retention index system for use by chemistry students to establish criteria for the optimal selection of gas chromatographic stationary phases. (TW)

Comprehensive two-dimensional liquid chromatography of therapeutic monoclonal antibody digests.

PubMed

Vanhoenacker, Gerd; Vandenheede, Isabel; David, Frank; Sandra, Pat; Sandra, Koen

2015-01-01

Comprehensive two-dimensional liquid chromatography (LC×LC) is here proposed as a novel tool for peptide mapping of therapeutic monoclonal antibodies in both R&D and routine (QA/QC) environments. This is illustrated by the analysis of the tryptic digest of trastuzumab (Herceptin) applying a commercially available two-dimensional 2D-LC system. Three different LC×LC combinations, i.e., strong cation-exchange × reversed-phase (SCX×RP), reversed-phase × reversed-phase (RP×RP), and hydrophilic interaction × reversed-phase (HILIC×RP), are reported. Detection was carried out using both UV detection (DAD) and mass spectrometry (MS). Several challenges related to the application of LC×LC in peptide mapping and the hyphenation to MS are addressed. The applicability of LC×LC in the assessment of identity, purity, and comparability is demonstrated by the analysis of different Herceptin innovator production batches, a Herceptin biosimilar in development and of stressed samples. The described methodology was shown to be precise in terms of peak volume and (2)D retention time opening interesting perspectives for use in QA/QC testing.

Analysis of Soft Drinks: UV Spectrophotometry, Liquid Chromatography, and Capillary Electrophoresis

NASA Astrophysics Data System (ADS)

McDevitt, Valerie L.; Rodriguez, Alejandra; Williams, Kathryn R.

1998-05-01

Instrumental analysis students analyze commercial soft drinks in three successive laboratory experiments. First, UV multicomponent analysis is used to determine caffeine and benzoic acid in Mello YelloTM using the spectrophotometer's software and manually by the simultaneous equations method. The following week, caffeine, benzoic acid and aspartame are determined in a variety of soft drinks by reversed-phase liquid chromatography using 45% methanol/55% aqueous phosphate, pH 3.0, as the mobile phase. In the third experiment, the same samples are analyzed by capillary electrophoresis using a pH 9.4 borate buffer. Students also determine the minimum detection limits for all three compounds by both LC and CE. The experiments demonstrate the analytical use and limitations of the three instruments. The reports and prelab quizzes also stress the importance of the chemistry of the three compounds, especially the relationships of acid/base behavior and polarity to the LC and CE separations.

Modeling of Shock Waves with Multiple Phase Transitions in Condensed Materials

NASA Astrophysics Data System (ADS)

Missonnier, Marc; Heuzé, Olivier

2006-07-01

When a shock wave crosses a solid material and subjects it to solid-solid or solid-liquid phase transition, related phenomena occur: shock splitting, and the corresponding released shock wave after reflection. Modelling of these phenomena raises physical and numerical issues. After shock loading, such materials can reach different kinds of states: single-phase states, binary-phase states, and triple points. The thermodynamic path can be studied and easily understood in the (V,E) or (V,S) planes. In the case of 3 phase tin (β,γ, and liquid) submitted to shock waves, seven states can occur: β,γ, liquid, β-γ, β-liquid, γ-liquid, and β-γ-liquid. After studying the thermodynamic properties with a complete 3-phase Equation of State, we show the existence of these seven states with a hydrodynamic simulation.

Multiphase, multicomponent parameter estimation for liquid and vapor fluxes in deep arid systems using hydrologic data and natural environmental tracers

USGS Publications Warehouse

Kwicklis, Edward M.; Wolfsberg, Andrew V.; Stauffer, Philip H.; Walvoord, Michelle Ann; Sully, Michael J.

2006-01-01

Multiphase, multicomponent numerical models of long-term unsaturated-zone liquid and vapor movement were created for a thick alluvial basin at the Nevada Test Site to predict present-day liquid and vapor fluxes. The numerical models are based on recently developed conceptual models of unsaturated-zone moisture movement in thick alluvium that explain present-day water potential and tracer profiles in terms of major climate and vegetation transitions that have occurred during the past 10 000 yr or more. The numerical models were calibrated using borehole hydrologic and environmental tracer data available from a low-level radioactive waste management site located in a former nuclear weapons testing area. The environmental tracer data used in the model calibration includes tracers that migrate in both the liquid and vapor phases (??D, ??18O) and tracers that migrate solely as dissolved solutes (Cl), thus enabling the estimation of some gas-phase as well as liquid-phase transport parameters. Parameter uncertainties and correlations identified during model calibration were used to generate parameter combinations for a set of Monte Carlo simulations to more fully characterize the uncertainty in liquid and vapor fluxes. The calculated background liquid and vapor fluxes decrease as the estimated time since the transition to the present-day arid climate increases. However, on the whole, the estimated fluxes display relatively little variability because correlations among parameters tend to create parameter sets for which changes in some parameters offset the effects of others in the set. Independent estimates on the timing since the climate transition established from packrat midden data were essential for constraining the model calibration results. The study demonstrates the utility of environmental tracer data in developing numerical models of liquid- and gas-phase moisture movement and the importance of considering parameter correlations when using Monte Carlo analysis to characterize the uncertainty in moisture fluxes. ?? Soil Science Society of America.

Phase transition analysis of V-shaped liquid crystal: Combined temperature-dependent FTIR and density functional theory approach

NASA Astrophysics Data System (ADS)

Singh, Swapnil; Singh, Harshita; Karthick, T.; Tandon, Poonam; Prasad, Veena

2018-01-01

Temperature-dependent Fourier transform infrared spectroscopy (FTIR) combined with density functional theory (DFT) is employed to study the mechanism of phase transitions of V-shaped bent-core liquid crystal. Since it has a large number of flexible bonds, one-dimensional potential energy scan (PES) was performed on the flexible bonds and predicted the most stable conformer I. A detailed analysis of vibrational normal modes of conformer I have been done on the basis of potential energy distribution. The good agreement between the calculated spectrum of conformer I and observed FTIR spectrum at room temperature validates our theoretical structure model. Furthermore, the prominent changes observed in the stretching vibrational bands of CH3/CH2, Cdbnd O, ring CC, ring CO, ring CH in-plane bending, and ring CH out-of-plane bending at Iso → nematic phase transition (at 155 °C) have been illustrated. However, the minor changes in the spectral features observed for the other phase transitions might be due to the shape or bulkiness of molecules. Combined FTIR and PES study beautifully explained the dynamics of the molecules, molecular realignment, H-bonding, and conformational changes at the phase transitions.

Observation of paramorphic phenomenon and non-tilted orthogonal smectic phases in hydrogen bonded ferroelectric liquid crystals for photonic applications

NASA Astrophysics Data System (ADS)

Subhasri, P.; Venugopal, D.; Jayaprakasam, R.; Chitravel, T.; Vijayakumar, V. N.

2018-06-01

A new class of hydrogen bonded ferroelectric liquid crystals (HBFLC) have been designed and synthesized by intermolecular hydrogen bonds between mesogenic 4-decyloxybenzoic acid (10OBA) and non-mesogenic (R)-(+)-Methylsuccinic acid (MSA) which have been confirmed through experimental and theoretical studies. Further, Mulliken population analysis clearly reveals that the existence of hydrogen bonds, strength and dynamic properties. Textural observation and its corresponding enthalpy values are analyzed by polarizing optical microscope (POM) and differential scanning calorimetry (DSC) respectively. Paramorphic changes in Sm C* phase due to the change of refractive index, which clearly reveal that the complex could be used for filtering action in photonic devices. The transition from lone pair to π* with large stabilization energy evidently exposes the chiral phases in the present HBFLC complex. Intermolecular interaction is analyzed by using natural bond orbital (NBO) studies. The highest energy in the HOMO-LUMO shows the stable phase in the HBFLC complex. Molecular structure of the HBFLC complex possesses the monoclinic which has been evinced through x-ray analysis. The randomly oriented bunch of homogeneous molecules in Sm A* phase of the HBFLC complex is reported.

Stability hierarchy between Piracetam forms I, II, and III from experimental pressure-temperature diagrams and topological inferences.

PubMed

Toscani, Siro; Céolin, René; Minassian, Léon Ter; Barrio, Maria; Veglio, Nestor; Tamarit, Josep-Lluis; Louër, Daniel; Rietveld, Ivo B

2016-01-30

The trimorphism of the active pharmaceutical ingredient piracetam is a famous case of polymorphism that has been frequently revisited by many researchers. The phase relationships between forms I, II, and III were ambiguous because they seemed to depend on the heating rate of the DSC and on the history of the samples or they have not been observed at all (equilibrium II-III). In the present paper, piezo-thermal analysis and high-pressure differential thermal analysis have been used to elucidate the positions of the different solid-solid and solid-liquid equilibria. The phase diagram, involving the three solid phases, the liquid phase and the vapor phase, has been constructed. It has been shown that form III is the high-pressure, low-temperature form and the stable form at room temperature. Form II is stable under intermediary conditions and form I is the low pressure, high temperature form, which possesses a stable melting point. The present paper demonstrates the strength of the topological approach based on the Clapeyron equation and the alternation rule when combined with high-pressure measurements. Copyright © 2015 Elsevier B.V. All rights reserved.

Investigation of local evaporation flux and vapor-phase pressure at an evaporative droplet interface.

PubMed

Duan, Fei; Ward, C A

2009-07-07

In the steady-state experiments of water droplet evaporation, when the throat was heating at a stainless steel conical funnel, the interfacial liquid temperature was found to increase parabolically from the center line to the rim of the funnel with the global vapor-phase pressure at around 600 Pa. The energy conservation analysis at the interface indicates that the energy required for evaporation is maintained by thermal conduction to the interface from the liquid and vapor phases, thermocapillary convection at interface, and the viscous dissipation globally and locally. The local evaporation flux increases from the center line to the periphery as a result of multiple effects of energy transport at the interface. The local vapor-phase pressure predicted from statistical rate theory (SRT) is also found to increase monotonically toward the interface edge from the center line. However, the average value of the local vapor-phase pressures is in agreement with the measured global vapor-phase pressure within the measured error bar.

Influence of storage conditions on the stability of monomeric anthocyanins studied by reversed-phase high-performance liquid chromatography.

PubMed

Morais, Helena; Ramos, Cristina; Forgács, Esther; Cserháti, Tibor; Oliviera, José

2002-04-25

The effect of light, storage time and temperature on the decomposition rate of monomeric anthocyanin pigments extracted from skins of grape (Vitis vinifera var. Red globe) was determined by reversed-phase high-performance liquid chromatography (RP-HPLC). The impact of various storage conditions on the pigment stability was assessed by stepwise regression analysis. RP-HPLC separated well the five anthocyanins identified and proved the presence of other unidentified pigments at lower concentrations. Stepwise regression analysis confirmed that the overall decomposition rate of monomeric anthocyanins, peonidin-3-glucoside and malvidin-3-glucoside significantly depended on the time and temperature of storage, the effect of storage time being the most important. The presence or absence of light exerted a negligible impact on the decomposition rate.

Improvement of the Processes of Liquid-Phase Epitaxial Growth of Nanoheteroepitaxial Structures

NASA Astrophysics Data System (ADS)

Maronchuk, I. I.; Sanikovich, D. D.; Potapkov, P. V.; Vel‧chenko, A. A.

2018-05-01

We have revealed the shortcomings of equipment and technological approaches in growing nanoheteroepitaxial structures with quantum dots by liquid-phase epitaxy. We have developed and fabricated a new vertical barreltype cassette for growing quantum dots and epitaxial layers of various thicknesses in one technological process. A physico-mathematical simulation has been carried out of the processes of liquid-phase epitaxial growth of quantumdimensional structures with the use of the program product SolidWorks (FlowSimulation program). Analysis has revealed the presence of negative factors influencing the growth process of the above structures. The mathematical model has been optimized, and the equipment has been modernized without additional experiments and measurements. The flow dynamics of the process gas in the reactor at various flow rates has been investigated. A method for tuning the thermal equipment has been developed. The calculated and experimental temperature distributions in the process of growing structures with high reproducibility are in good agreement, which confirms the validity of the modernization made.

Analysis of triacylglycerols on porous graphitic carbon by high temperature liquid chromatography.

PubMed

Merelli, Bérangère; De Person, Marine; Favetta, Patrick; Lafosse, Michel

2007-07-20

The retention behaviour of several triacylglycerols (TAGs) and fats on Hypercarb, a porous graphitic carbon column (PGC), was investigated in liquid chromatography (LC) under isocratic elution mode with an evaporative light scattering detector (ELSD). Mixtures of chloroform/isopropanol were selected as mobile phase for a suitable retention time to study the influence of temperature. The retention was different between PGC and non-aqueous reversed phase liquid chromatography (NARP-LC) on octadecyl phase. The retention of TAGs was investigated in the interval 30-70 degrees C. Retention was greatly affected by temperature: it decreases as the column temperature increases. Selectivity of TAGs was also slightly influenced by the temperature. Moreover, this chromatographic method is compatible with a mass spectrometer (MS) detector by using atmospheric pressure chemical ionisation (APCI): same fingerprints of cocoa butter and shea butter were obtained with LC-ELSD and LC-APCI-MS. These preliminary results showed that the PGC column could be suitable to separate quickly triacylglycerols in high temperature conditions coupled with ELSD or MS detector.

Surface confined ionic liquid as a stationary phase for HPLC

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

Wang, Qian; Baker, Gary A; Baker, Sheila N

Trimethoxysilane ionosilane derivatives of room temperature ionic liquids based on alkylimidazolium bromides were synthesized for attachment to silica support material. The derivatives 1-methyl-3-(trimethoxysilylpropyl)imidazolium bromide and 1-butyl-3-(trimethoxysilylpropyl)imidazolium bromide were used to modify the surface of 3 {micro}m diameter silica particles to act as the stationary phase for HPLC. The modified particles were characterized by thermogravimetric analysis (TGA) and {sup 13}C and {sup 29}Si NMR spectroscopies. The surface modification procedure rendered particles with a surface coverage of 0.84 {micro}mol m{sup -2} for the alkylimidazolium bromide. The ionic liquid moiety was predominantly attached to the silica surface through two siloxane bonds of themore » ionosilane derivative (63%). Columns packed with the modified silica material were tested under HPLC conditions. Preliminary evaluation of the stationary phase for HPLC was performed using aromatic carboxylic acids as model compounds. The separation mechanism appears to involve multiple interactions including ion exchange, hydrophobic interaction, and other electrostatic interactions.« less

Evaporative Mass Transfer Behavior of a Complex Immiscible Liquid

PubMed Central

McColl, Colleen M.; Johnson, Gwynn R.; Brusseau, Mark L.

2010-01-01

A series of laboratory experiments was conducted with a multiple-component immiscible liquid, collected from the Picillo Farm Superfund Site in Rhode Island, to examine liquid-vapor mass-transfer behavior. The immiscible liquid, which comprises solvents, oils, pesticides, PCBs, paint sludges, explosives, and other compounds, was characterized using gas chromatography and gas chromatography/mass spectrometry to determine mole fractions of selected constituents. Batch experiments were conducted to evaluate equilibrium phase-partitioning behavior. Two sets of air-stripping column studies were conducted to examine the mass-transfer dynamics of five selected target compounds present in the immiscible-liquid mixture. One set of column experiments was designed to represent a system with free-phase immiscible liquid present; the other was designed to represent a system with a residual phase of immiscible liquid. Initial elution behavior of all target components generally appeared to be ideal for both systems, as the initial vapor-phase concentrations were similar to vapor-phase concentrations measured for the batch experiment and those estimated using Raoult’s law (incorporating the immiscible-liquid composition data). Later-stage removal of 1,2-dichlorobenzene appeared to be rate limited for the columns containing free-phase immiscible liquid and no porous medium. Conversely, evaporative mass transfer appeared to be ideal throughout the experiment conducted with immiscible liquid distributed relatively uniformly as a residual phase within a sandy porous medium. PMID:18614196

Evaporative mass transfer behavior of a complex immiscible liquid.

PubMed

McColl, Colleen M; Johnson, Gwynn R; Brusseau, Mark L

2008-09-01

A series of laboratory experiments was conducted with a multiple-component immiscible liquid, collected from the Picillo Farm Superfund Site in Rhode Island, to examine liquid-vapor mass-transfer behavior. The immiscible liquid, which comprises solvents, oils, pesticides, PCBs, paint sludges, explosives, and other compounds, was characterized using gas chromatography and gas chromatography/mass spectrometry to determine mole fractions of selected constituents. Batch experiments were conducted to evaluate equilibrium phase-partitioning behavior. Two sets of air-stripping column studies were conducted to examine the mass-transfer dynamics of five selected target compounds present in the immiscible-liquid mixture. One set of column experiments was designed to represent a system with free-phase immiscible liquid present; the other was designed to represent a system with a residual phase of immiscible liquid. Initial elution behavior of all target components generally appeared to be ideal for both systems, as the initial vapor-phase concentrations were similar to vapor-phase concentrations measured for the batch experiment and those estimated using Raoult's law (incorporating the immiscible-liquid composition data). Later-stage removal of 1,2-dichlorobenzene appeared to be rate limited for the columns containing free-phase immiscible liquid and no porous medium. Conversely, evaporative mass transfer appeared to be ideal throughout the experiment conducted with immiscible liquid distributed relatively uniformly as a residual phase within a sandy porous medium.

A Novel Liquid-Liquid Transition in Undercooled Ti-Zr-Ni Liquids

NASA Technical Reports Server (NTRS)

Lee, G. W.; Gangopadhyay, A. K.; Kelton, K. F.; Bradshaw, R. C.; Hyers, R. W.; Rathz, T. J.; Rogers, J. R.

2004-01-01

If crystallization can be avoided, liquids enter a metastable (undercooled) state below their equilibrium liquidus temperatures, T(sub l), finally 'freezing' into a glass below a characteristic temperature called the glass transition temperature, T(sub g). In rare cases, the undercooled liquid may undergo a liquid-liquid phase transition (liquid polymorphism) before entering the glassy state. This has been suggested from experimental studies of H2O and Si. Such phase transitions have been predicted in some stable liquids, ie. above T(sub l) at atmospheric pressure, for SiO2 and BeF2, but these have not been verified experimentally. They have been observed in liquids of P, Si and C, but only under high pressure. In this letter we present the first experimental evidence for a phase transition in a low viscosity metallic liquid that is driven by an approach to a constant entropy configuration state and correlated with a growing icosahedral order in the liquid. A maximum in the specific heat at constant pressure, similar to what is normally observed near T(sub g), is reported for undercooled liquids of quasicrystal-forming Ti-Zr-Ni alloys. A two-state excitation model that includes cooperativity by incorporating a temperature-dependent excitation energy, fits the specific heat data well, signaling a phase transition. An inflection in the liquid density with decreasing temperature instead of a discontinuity indicates that this is not a typical first order phase transition; it could be a weakly first order or higher order transition. While showing many similarities to a glass transition, this liquid-liquid phase transition occurs in a mobile liquid, making it novel.

μ-'Diving suit' for liquid-phase high-Q resonant detection.

PubMed

Yu, Haitao; Chen, Ying; Xu, Pengcheng; Xu, Tiegang; Bao, Yuyang; Li, Xinxin

2016-03-07

A resonant cantilever sensor is, for the first time, dressed in a water-proof 'diving suit' for real-time bio/chemical detection in liquid. The μ-'diving suit' technology can effectively avoid not only unsustainable resonance due to heavy liquid-damping, but also inevitable nonspecific adsorption on the cantilever body. Such a novel technology ensures long-time high-Q resonance of the cantilever in solution environment for real-time trace-concentration bio/chemical detection and analysis. After the formation of the integrated resonant micro-cantilever, a patterned photoresist and hydrophobic parylene thin-film are sequentially formed on top of the cantilever as sacrificial layer and water-proof coat, respectively. After sacrificial-layer release, an air gap is formed between the parylene coat and the cantilever to protect the resonant cantilever from heavy liquid damping effect. Only a small sensing-pool area, located at the cantilever free-end and locally coated with specific sensing-material, is exposed to the liquid analyte for gravimetric detection. The specifically adsorbed analyte mass can be real-time detected by recording the frequency-shift signal. In order to secure vibration movement of the cantilever and, simultaneously, reject liquid leakage from the sensing-pool region, a hydrophobic parylene made narrow slit structure is designed surrounding the sensing-pool. The anti-leakage effect of the narrow slit and damping limited resonance Q-factor are modelled and optimally designed. Integrated with electro-thermal resonance excitation and piezoresistive frequency readout, the cantilever is embedded in a micro-fluidic chip to form a lab-chip micro-system for liquid-phase bio/chemical detection. Experimental results show the Q-factor of 23 in water and longer than 20 hours liquid-phase continuous working time. Loaded with two kinds of sensing-materials at the sensing-pools, two types of sensing chips successfully show real-time liquid-phase detection to ppb-level organophosphorous pesticide of acephate and E.coli DH5α in PBS, respectively. The proposed method fundamentally solves the long-standing problem of being unable to operate a resonant micro-sensor in liquid well.

Pressure Induced Liquid-to-Liquid Transition in Zr-based Supercooled Melts and Pressure Quenched Glasses.

PubMed

Dmowski, W; Gierlotka, S; Wang, Z; Yokoyama, Y; Palosz, B; Egami, T

2017-07-26

Through high-energy x-ray diffraction and atomic pair density function analysis we find that Zr-based metallic alloy, heated to the supercooled liquid state under hydrostatic pressure and then quenched to room temperature, exhibits a distinct glassy structure. The PDF indicates that the Zr-Zr distances in this glass are significantly reduced compared to those quenched without pressure. Annealing at the glass transition temperature at ambient pressure reverses structural changes and the initial glassy state is recovered. This result suggests that pressure causes a liquid-to-liquid phase transition in this metallic alloy supercooled melt. Such a pressure induced transition is known for covalent liquids, but has not been observed for metallic liquids. The High Pressure Quenched glasses are stable in ambient conditions after decompression.

Proper Orthogonal Decomposition on Experimental Multi-phase Flow in a Pipe

NASA Astrophysics Data System (ADS)

Viggiano, Bianca; Tutkun, Murat; Cal, Raúl Bayoán

2016-11-01

Multi-phase flow in a 10 cm diameter pipe is analyzed using proper orthogonal decomposition. The data were obtained using X-ray computed tomography in the Well Flow Loop at the Institute for Energy Technology in Kjeller, Norway. The system consists of two sources and two detectors; one camera records the vertical beams and one camera records the horizontal beams. The X-ray system allows measurement of phase holdup, cross-sectional phase distributions and gas-liquid interface characteristics within the pipe. The mathematical framework in the context of multi-phase flows is developed. Phase fractions of a two-phase (gas-liquid) flow are analyzed and a reduced order description of the flow is generated. Experimental data deepens the complexity of the analysis with limited known quantities for reconstruction. Comparison between the reconstructed fields and the full data set allows observation of the important features. The mathematical description obtained from the decomposition will deepen the understanding of multi-phase flow characteristics and is applicable to fluidized beds, hydroelectric power and nuclear processes to name a few.

Stable Isotope Quantitative N-Glycan Analysis by Liquid Separation Techniques and Mass Spectrometry.

PubMed

Mittermayr, Stefan; Albrecht, Simone; Váradi, Csaba; Millán-Martín, Silvia; Bones, Jonathan

2017-01-01

Liquid phase separation analysis and subsequent quantitation remains a challenging task for protein-derived oligosaccharides due to their inherent structural complexity and diversity. Incomplete resolution or co-detection of multiple glycan species complicates peak area-based quantitation and associated statistical analysis when optical detection methods are used. The approach outlined herein describes the utilization of stable isotope variants of commonly used fluorescent tags that allow for mass-based glycan identification and relative quantitation following separation by liquid chromatography (LC) or capillary electrophoresis (CE). Comparability assessment of glycoprotein-derived oligosaccharides is performed by derivatization with commercially available isotope variants of 2-aminobenzoic acid or aniline and analysis by LC- and CE-mass spectrometry. Quantitative information is attained from the extracted ion chromatogram/electropherogram ratios generated from the light and heavy isotope clusters.

Liquid phase sintering of silicon carbide

DOEpatents

Cutler, R.A.; Virkar, A.V.; Hurford, A.C.

1989-05-09

Liquid phase sintering is used to densify silicon carbide based ceramics using a compound comprising a rare earth oxide and aluminum oxide to form liquids at temperatures in excess of 1,600 C. The resulting sintered ceramic body has a density greater than 95% of its theoretical density and hardness in excess of 23 GPa. Boron and carbon are not needed to promote densification and silicon carbide powder with an average particle size of greater than one micron can be densified via the liquid phase process. The sintered ceramic bodies made by the present invention are fine grained and have secondary phases resulting from the liquid phase. 4 figs.

Liquid phase sintering of silicon carbide

DOEpatents

Cutler, Raymond A.; Virkar, Anil V.; Hurford, Andrew C.

1989-01-01

Liquid phase sintering is used to densify silicon carbide based ceramics using a compound comprising a rare earth oxide and aluminum oxide to form liquids at temperatures in excess of 1600.degree. C. The resulting sintered ceramic body has a density greater than 95% of its theoretical density and hardness in excess of 23 GPa. Boron and carbon are not needed to promote densification and silicon carbide powder with an average particle size of greater than one micron can be densified via the liquid phase process. The sintered ceramic bodies made by the present invention are fine grained and have secondary phases resulting from the liquid phase.

Structure and phase behavior of a confined nanodroplet composed of the flexible chain molecules.

PubMed

Kim, Soon-Chul; Kim, Eun-Young; Seong, Baek-Seok

2011-04-28

A polymer density functional theory has been employed for investigating the structure and phase behaviors of the chain polymer, which is modelled as the tangentially connected sphere chain with an attractive interaction, inside the nanosized pores. The excess free energy of the chain polymer has been approximated as the modified fundamental measure-theory for the hard spheres, the Wertheim's first-order perturbation for the chain connectivity, and the mean-field approximation for the van der Waals contribution. For the value of the chemical potential corresponding to a stable liquid phase in the bulk system and a metastable vapor phase, the flexible chain molecules undergo the liquid-vapor transition as the pore size is reduced; the vapor is the stable phase at small volume, whereas the liquid is the stable phase at large volume. The wide liquid-vapor coexistence curve, which explains the wide range of metastable liquid-vapor states, is observed at low temperature. The increase of temperature and decrease of pore size result in a narrowing of liquid-vapor coexistence curves. The increase of chain length leads to a shift of the liquid-vapor coexistence curve towards lower values of chemical potential. The coexistence curves for the confined phase diagram are contained within the corresponding bulk liquid-vapor coexistence curve. The equilibrium capillary phase transition occurs at a higher chemical potential than in the bulk phase.

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.

On the accuracy of the MB-pol many-body potential for water: Interaction energies, vibrational frequencies, and classical thermodynamic and dynamical properties from clusters to liquid water and ice

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

Reddy, Sandeep K.; Straight, Shelby C.; Bajaj, Pushp

The MB-pol many-body potential has recently emerged as an accurate molecular model for water simulations from the gas to the condensed phase. In this study, the accuracy of MB-pol is systematically assessed across the three phases of water through extensive comparisons with experimental data and high-level ab initio calculations. Individual many-body contributions to the interaction energies as well as vibrational spectra of water clusters calculated with MB-pol are in excellent agreement with reference data obtained at the coupled cluster level. Several structural, thermodynamic, and dynamical properties of the liquid phase at atmospheric pressure are investigated through classical molecular dynamics simulationsmore » as a function of temperature. The structural properties of the liquid phase are in nearly quantitative agreement with X-ray diffraction data available over the temperature range from 268 to 368 K. The analysis of other thermodynamic and dynamical quantities emphasizes the importance of explicitly including nuclear quantum effects in the simulations, especially at low temperature, for a physically correct description of the properties of liquid water. Furthermore, both densities and lattice energies of several ice phases are also correctly reproduced by MB-pol. Following a recent study of DFT models for water, a score is assigned to each computed property, which demonstrates the high and, in many respects, unprecedented accuracy of MB-pol in representing all three phases of water. Published by AIP Publishing.« less

On the accuracy of the MB-pol many-body potential for water: Interaction energies, vibrational frequencies, and classical thermodynamic and dynamical properties from clusters to liquid water and ice [How good is the MB-pol many-body potential for water?

DOE PAGES

Reddy, Sandeep K.; Straight, Shelby C.; Bajaj, Pushp; ...

2016-11-17

The MB-pol many-body potential has recently emerged as an accurate molecular model for water simulations from the gas to the condensed phase. Here, the accuracy of MB-pol is systematically assessed across the three phases of water through extensive comparisons with experimental data and high-level ab initio calculations. Individual many-body contributions to the interaction energies as well as vibrational spectra of water clusters calculated with MB-pol are in excellent agreement with reference data obtained at the coupled cluster level. We investigate several structural, thermodynamic, and dynamical properties of the liquid phase at atmospheric pressure through classical molecular dynamics simulations as amore » function of temperature. Furthermore, the structural properties of the liquid phase are in nearly quantitative agreement with X-ray diffraction data available over the temperature range from 268 to 368 K. The analysis of other thermodynamic and dynamical quantities emphasizes the importance of explicitly including nuclear quantum effects in the simulations, especially at low temperature, for a physically correct description of the properties of liquid water. Furthermore, both densities and lattice energies of several ice phases are also correctly reproduced by MB-pol. Following a recent study of DFT models for water, a score is assigned to each computed property, which demonstrates the high and, in many respects, unprecedented accuracy of MB-pol in representing all three phases of water.« less

On the accuracy of the MB-pol many-body potential for water: Interaction energies, vibrational frequencies, and classical thermodynamic and dynamical properties from clusters to liquid water and ice [How good is the MB-pol many-body potential for water?

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

Reddy, Sandeep K.; Straight, Shelby C.; Bajaj, Pushp

The MB-pol many-body potential has recently emerged as an accurate molecular model for water simulations from the gas to the condensed phase. Here, the accuracy of MB-pol is systematically assessed across the three phases of water through extensive comparisons with experimental data and high-level ab initio calculations. Individual many-body contributions to the interaction energies as well as vibrational spectra of water clusters calculated with MB-pol are in excellent agreement with reference data obtained at the coupled cluster level. We investigate several structural, thermodynamic, and dynamical properties of the liquid phase at atmospheric pressure through classical molecular dynamics simulations as amore » function of temperature. Furthermore, the structural properties of the liquid phase are in nearly quantitative agreement with X-ray diffraction data available over the temperature range from 268 to 368 K. The analysis of other thermodynamic and dynamical quantities emphasizes the importance of explicitly including nuclear quantum effects in the simulations, especially at low temperature, for a physically correct description of the properties of liquid water. Furthermore, both densities and lattice energies of several ice phases are also correctly reproduced by MB-pol. Following a recent study of DFT models for water, a score is assigned to each computed property, which demonstrates the high and, in many respects, unprecedented accuracy of MB-pol in representing all three phases of water.« less

49 CFR 179.400-19 - Valves and gages.

Code of Federal Regulations, 2014 CFR

2014-10-01

... control of vapor phase pressure, vapor phase venting, liquid transfer and liquid flow rates. All valves... within suitable protective housings. A liquid level gage and a vapor phase pressure gage must be provided... Liquid Tank Car Tanks and Seamless Steel Tanks (Classes DOT-113 and 107A) § 179.400-19 Valves and gages...

49 CFR 179.400-19 - Valves and gages.

Code of Federal Regulations, 2012 CFR

2012-10-01

... control of vapor phase pressure, vapor phase venting, liquid transfer and liquid flow rates. All valves... within suitable protective housings. A liquid level gage and a vapor phase pressure gage must be provided... Liquid Tank Car Tanks and Seamless Steel Tanks (Classes DOT-113 and 107A) § 179.400-19 Valves and gages...

49 CFR 179.400-19 - Valves and gages.

Code of Federal Regulations, 2013 CFR

2013-10-01

... control of vapor phase pressure, vapor phase venting, liquid transfer and liquid flow rates. All valves... within suitable protective housings. A liquid level gage and a vapor phase pressure gage must be provided... Liquid Tank Car Tanks and Seamless Steel Tanks (Classes DOT-113 and 107A) § 179.400-19 Valves and gages...

Evaluating the Liquid Liquid Phase Transition Hypothesis of Supercoooled Water

NASA Astrophysics Data System (ADS)

Limmer, David; Chandler, David

2011-03-01

To explain the anomalous behavior of supercooled water it has been conjectured that buried within an experimentally inaccessible region of liquid water's phase diagram there exists a second critical point, which is the terminus of a first order transition line between two distinct liquid phases. The so-called liquid-liquid phase transition (LLPT) has since generated much study, though to date there is no consensus on its existence. In this talk, we will discuss our efforts to systematically study the metastable phase diagram of supercooled water through computer simulation. By employing importance-sampling techniques, we have calculated free energies as a function of the density and long-range order to determine unambiguously if two distinct liquid phases exist. We will argue that, contrary to the LLPT hypothesis, the observed phenomenology can be understood as a consequence of the limit of stability of the liquid far away from coexistence. Our results suggest that homogeneous nucleation is the cause of the increased fluctuations present upon supercooling. Further we will show how this understanding can be extended to explain experimental observations of hysteresis in confined supercooled water systems.

CRYOCHEM, Thermodynamic Model for Cryogenic Chemical Systems: Solid-Vapor and Solid-Liquid-Vapor Phase Equilibria Toward Applications on Titan and Pluto

NASA Astrophysics Data System (ADS)

Tan, S. P.; Kargel, J. S.; Adidharma, H.; Marion, G. M.

2014-12-01

Until in-situ measurements can be made regularly on extraterrestrial bodies, thermodynamic models are the only tools to investigate the properties and behavior of chemical systems on those bodies. The resulting findings are often critical in describing physicochemical processes in the atmosphere, surface, and subsurface in planetary geochemistry and climate studies. The extremely cold conditions on Triton, Pluto and other Kuiper Belt Objects, and Titan introduce huge non-ideality that prevents conventional models from performing adequately. At such conditions, atmospheres as a whole—not components individually—are subject to phase equilibria with their equilibrium solid phases or liquid phases or both. A molecular-based thermodynamic model for cryogenic chemical systems, referred to as CRYOCHEM, the development of which is still in progress, was shown to reproduce the vertical composition profile of Titan's atmospheric methane measured by the Huygens probe (Tan et al., Icarus 2013, 222, 53). Recently, the model was also used to describe Titan's global circulation where the calculated composition of liquid in Ligeia Mare is consistent with the bathymetry and microwave absorption analysis of T91 Cassini fly-by data (Tan et al., 2014, submitted). Its capability to deal with equilibria involving solid phases has also been demonstrated (Tan et al., Fluid Phase Equilib. 2013, 360, 320). With all those previous works done, our attention is now shifting to the lower temperatures in Titan's tropopause and on Pluto's surface, where much technical development remains for CRYOCHEM to assure adequate performance at low temperatures. In these conditions, solid-vapor equilibrium (SVE) is the dominant phase behavior that determines the composition of the atmosphere and the existing ices. Another potential application is for the subsurface phase equilibrium, which also involves liquid, thus three-phase equilibrium: solid-liquid-vapor (SLV). This presentation will discuss the current state of CRYOCHEM in representing the SVE and SLV of chemical systems at temperatures and pressures relevant to Titan's tropopause and Pluto and the upper crusts of these objects.

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.

Quantum Liquid Crystal Phases in Strongly Correlated Fermionic Systems

ERIC Educational Resources Information Center

Sun, Kai

2009-01-01

This thesis is devoted to the investigation of the quantum liquid crystal phases in strongly correlated electronic systems. Such phases are characterized by their partially broken spatial symmetries and are observed in various strongly correlated systems as being summarized in Chapter 1. Although quantum liquid crystal phases often involve…

Dispersive liquid-liquid microextraction for the determination of vitamins D and K in foods by liquid chromatography with diode-array and atmospheric pressure chemical ionization-mass spectrometry detection.

PubMed

Viñas, Pilar; Bravo-Bravo, María; López-García, Ignacio; Hernández-Córdoba, Manuel

2013-10-15

A simple and rapid method was developed using reversed-phase liquid chromatography (LC) with both diode array (DAD) and atmospheric pressure chemical ionization mass spectrometric (APCI-MS) detection, for the simultaneous analysis of the vitamins ergocalciferol (D2), cholecalciferol (D3), phylloquinone (K1), menaquinone-4 (K2) and a synthetic form of vitamin K, menadione (K3). The Taguchi experimental method, an orthogonal array design (OAD), was used to optimize an efficient and clean preconcentration step based on dispersive liquid-liquid microextraction (DLLME). A factorial design was applied with six factors and three levels for each factor, namely, carbon tetrachloride volume, methanol volume, aqueous sample volume, pH of sample, sodium chloride concentration and time of the centrifugation step. The DLLME optimized procedure consisted of rapidly injecting 3 mL of acetonitrile (disperser solvent) containing 150 µL carbon tetrachloride (extraction solvent) into the aqueous sample, thereby forming a cloudy solution. Phase separation was performed by centrifugation, and the sedimented phase was evaporated with nitrogen, reconstituted with 50 µL of acetonitrile, and injected. The LC analyses were carried out using a mobile phase composed of acetonitrile, 2-propanol and water, under gradient elution. Quantification was carried out by the standard additions method. The APCI-MS spectra, in combination with UV spectra, permitted the correct identification of compounds in the food samples. The method was validated according to international guidelines and using a certified reference material. The validated method was applied for the analysis of vitamins D and K in infant foods and several green vegetables. There was little variability in the forms of vitamin K present in vegetables, with the most abundant vitamer in all the samples being phylloquinone, while menadione could not be detected. Conversely, cholecalciferol, which is present in food of animal origin, was the main form in infant foods, while ergocalciferol was not detected. Copyright © 2013 Elsevier B.V. All rights reserved.

Two-step ion-exchange chromatographic purification combined with reversed-phase chromatography to isolate C-peptide for mass spectrometric analysis.

PubMed

Kabytaev, Kuanysh; Durairaj, Anita; Shin, Dmitriy; Rohlfing, Curt L; Connolly, Shawn; Little, Randie R; Stoyanov, Alexander V

2016-02-01

A liquid chromatography with mass spectrometry on-line platform that includes the orthogonal techniques of ion exchange and reversed phase chromatography is applied for C-peptide analysis. Additional improvement is achieved by the subsequent application of cation- and anion-exchange purification steps that allow for isolating components that have their isoelectric points in a narrow pH range before final reversed-phase mass spectrometry analysis. The utility of this approach for isolating fractions in the desired "pI window" for profiling complex mixtures is discussed. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The shape and dynamics of the generation of the splash forms in single-phase systems after drop hitting

NASA Astrophysics Data System (ADS)

Sochan, Agata; Beczek, Michał; Mazur, Rafał; RyŻak, Magdalena; Bieganowski, Andrzej

2018-02-01

The splash phenomenon is being increasingly explored with the use of modern measurement tools, including the high-speed cameras. Recording images at a rate of several thousand frames per second facilitates parameterization and description of the dynamics of splash phases. This paper describes the impact of a single drop of a liquid falling on the surface of the same liquid. Three single-phase liquid systems, i.e., water, petrol, and diesel fuel, were examined. The falling drops were characterized by different kinetic energy values depending on the height of the fall, which ranged from 0.1 to 7.0 m. Four forms, i.e., waves, crowns, semi-closed domes, and domes, were distinguished depending on the drop energy. The analysis of the recorded images facilitated determination of the static and dynamic parameters of each form, e.g., the maximum height of each splash form, the width of the splash form at its maximum height, and the rate of growth of the splash form. We, Re, Fr, and K numbers were determined for all analyzed liquid systems. On the basis of the obtained values of dimensionless numbers, the areas of occurrence of characteristic splash forms were separated.

Quantitative analysis of aldehydes in canned vegetables using static headspace-gas chromatography-mass spectrometry.

PubMed

Serrano, María; Gallego, Mercedes; Silva, Manuel

2017-11-17

Volatile aldehydes appear in canned vegetables as constituents and some of them can also be present as disinfection by-products (DBPs) because of the contact between vegetables and treated water. This paper describes two static headspace-gas chromatography-mass spectrometry (SHS-GC-MS) methods to determine 15 aldehydes in both the solid and the liquid phases of canned vegetables. The treatment for both phases of samples was carried out simultaneously into an SHS unit, including the leaching of the aldehydes (from the vegetable), their derivatization and volatilization of the oximes formed. Detection limits were obtained within the range of 15-400μg/kg and 3-40μg/L for aldehydes in the solid and the liquid phases of the food, respectively. The relative standard deviation was lower than 7% -for the whole array of the target analytes-, the trueness evaluated by recovery experiments provided %recoveries between 89 and 99% and short- and long-term stability studies indicated there was no significant variation in relative peak areas of all aldehydes in both phases of canned vegetables after their storing at 4°C for two weeks. The study of the origin of the 15 aldehydes detected between both phases of canned vegetables showed that: i) the presence of 13 aldehydes -at average concentrations of 2.2-39μg/kg and 0.25-71μg/L for the solid and the liquid phases, respectively- is because they are natural constituents of vegetables; and ii) the presence of glyoxal and methylglyoxal -which are mainly found in the liquid phase (average values, 1.4-4.1μg/L)- is ascribed to the use of treated water, thereby being DBPs. Copyright © 2017 Elsevier B.V. All rights reserved.

Dispersive micro-solid phase extraction combined with dispersive liquid-liquid microextraction for speciation analysis of antimony by electrothermal vaporization inductively coupled plasma mass spectrometry

NASA Astrophysics Data System (ADS)

Chen, Shizhong; Zhu, Shengping; Lu, Dengbo

2018-01-01

A method was developed for speciation analysis of antimony by electrothermal vaporization inductively coupled plasma mass spectrometry (ETV-ICP-MS) after preconcentration/separation using dispersive micro-solid phase extraction (DMSPE) and dispersive liquid-liquid micro-extraction (DLLME). In DMSPE, titanium dioxide nanofibers were used for preconcentration and separation of analytes. The upper aqueous phase and elution solution from DMSPE were used for further preconcentration and separation of Sb(III) and Sb(V) by DLLME without any pre-oxidation or pre-reduction operation, respectively. The extracts from DLLME were used for ETV-ICP-MS determination with APDC as a chemical modifier. Under optimal conditions, the detection limits of this method were 0.019 and 0.025 pg mL- 1 with relative standard deviations of 5.7% and 6.9% for Sb(III) and Sb(V) (c = 1.0 ng mL- 1, n = 9), respectively. This method was applied for speciation analysis of Sb and its distribution in the tea leaves and the tea infusion, including total, suspended, soluble, organic and inorganic Sb as well as Sb(III) and Sb(V). The results showed that the contents of Sb are 62.7, 12.9 and 47.3 ng g- 1 in the tea leaves, tea residue and tea soup, respectively; those of soluble, organic, inorganic, Sb(III) and Sb(V) are 0.41, 0.11, 0.29, 0.21 and 0.07 ng mL- 1 in the tea soup, respectively. A certified reference material of tea leaves (GBW 07605) was analyzed by this method with satisfactory results.

Dynamic and magneto-optic properties of bent-core liquid crystals

NASA Astrophysics Data System (ADS)

Salili, Seyyed Muhammad

In this work, we describe dynamic behavior of free-standing bent-core liquid crystal filaments under dilative and axial compressive stresses in the B7 phase. We found that such filaments demonstrate very complex structures depending on the filament's temperature relative to the isotropic phase, initial filament thickness, and velocity at which the filament is pulled or compressed. We also present our experimental methods, results and analysis of the rupture and recoil properties of several bent-core liquid crystal filaments, anticipating that they may serve as a model system for complex biological fibers. After that, we systematically describe rheological measurements for dimeric liquid crystal compounds. We studied the shear-induced alignment properties, measured the viscoelastic properties as a function of temperature, shear rate, stress and frequency, and compared the results with the rheological properties of conventional chiral nematic and smectic phases. Then we present results of chiral nematic liquid crystals composed of flexible dimer molecules subject to large DC magnetic fields between 0 and 31T. We observe that these fields lead to selective reflection of light depending on temperature and magnetic field. The band of reflected wavelengths can be tuned from ultraviolet to beyond the IR-C band. A similar effect induced by electric fields has been presented previously, and was explained by a field-induced oblique-heliconical director deformation in accordance with early theoretical predictions. Finally, we report an unprecedented magnetic field-induced shifts of the isotropic-nematic phase transition temperature observed in liquid crystal dimers where two rigid linear mesogens are linked by flexible chains of either even- or odd-numbered hydrocarbon groups. This effect is explained in terms of quenching of the thermal fluctuations and decrease of the average bend angle of molecules in the odd-numbered dimers.

Study of the influence of surfactants on the transfer of gases into liquids by inverse gas chromatography.

PubMed

Atta, Khan Rashid; Gavril, Dimitrios; Loukopoulos, Vassilios; Karaiskakis, George

2004-01-16

The experimental technique of the reversed-flow version of inverse gas chromatography was applied for the study of effects of surfactants in reducing air-water exchange rates. The vinyl chloride (VC)-water system was used as a model, which is of great importance in environmental chemistry. Using suitable mathematical analysis, various physicochemical quantities were calculated, among which the most significant are: Partition coefficients of the VC gas between the surfactant interface and the carrier gas nitrogen, as well as between the bulk of the water + surfactant solution and the carrier gas nitrogen, overall mass transfer coefficients of VC in the liquid (water + surfactant) and the gas (nitrogen) phases, water and surfactant film transfer coefficients, nitrogen, water and surfactant phase resistances for the transfer of VC into the water solution, relative resistance of surfactant in the transfer of VC into the bulk of solution, exchange velocity of VC between nitrogen and the liquid solution, and finally the thickness of the surfactant stagnant film in the liquid phase, according to the three phase resistance model. From the variation of the above parameters with the surfactant's concentration, important conclusions concerning the effects of surfactants on the transfer of a gas at the air-liquid interface, as well as to the bulk of the liquid were extracted. An interesting finding of this work was also that by successive addition of surfactant, the critical micelle concentration of surfactant was obtained, after which follows a steady-state for the transfer of the gas into the water body, which could be attributed to the transition from mono- to multi-layer state.

Modeling, design, packing and experimental analysis of liquid-phase shear-horizontal surface acoustic wave sensors

NASA Astrophysics Data System (ADS)

Pollard, Thomas B

Recent advances in microbiology, computational capabilities, and microelectromechanical-system fabrication techniques permit modeling, design, and fabrication of low-cost, miniature, sensitive and selective liquid-phase sensors and lab-on-a-chip systems. Such devices are expected to replace expensive, time-consuming, and bulky laboratory-based testing equipment. Potential applications for devices include: fluid characterization for material science and industry; chemical analysis in medicine and pharmacology; study of biological processes; food analysis; chemical kinetics analysis; and environmental monitoring. When combined with liquid-phase packaging, sensors based on surface-acoustic-wave (SAW) technology are considered strong candidates. For this reason such devices are focused on in this work; emphasis placed on device modeling and packaging for liquid-phase operation. Regarding modeling, topics considered include mode excitation efficiency of transducers; mode sensitivity based on guiding structure materials/geometries; and use of new piezoelectric materials. On packaging, topics considered include package interfacing with SAW devices, and minimization of packaging effects on device performance. In this work novel numerical models are theoretically developed and implemented to study propagation and transduction characteristics of sensor designs using wave/constitutive equations, Green's functions, and boundary/finite element methods. Using developed simulation tools that consider finite-thickness of all device electrodes, transduction efficiency for SAW transducers with neighboring uniform or periodic guiding electrodes is reported for the first time. Results indicate finite electrode thickness strongly affects efficiency. Using dense electrodes, efficiency is shown to approach 92% and 100% for uniform and periodic electrode guiding, respectively; yielding improved sensor detection limits. A numerical sensitivity analysis is presented targeting viscosity using uniform-electrode and shear-horizontal mode configurations on potassium-niobate, langasite, and quartz substrates. Optimum configurations are determined yielding maximum sensitivity. Results show mode propagation-loss and sensitivity to viscosity are correlated by a factor independent of substrate material. The analysis is useful for designing devices meeting sensitivity and signal level requirements. A novel, rapid and precise microfluidic chamber alignment/bonding method was developed for SAW platforms. The package is shown to have little effect on device performance and permits simple macrofluidic interfacing. Lastly, prototypes were designed, fabricated, and tested for viscosity and biosensor applications; results show ability to detect as low as 1% glycerol in water and surface-bound DNA crosslinking.

Analysis of holographic polymer-dispersed liquid crystals (HPDLCs) for tunable low frequency diffractive optical elements recording

NASA Astrophysics Data System (ADS)

Fernández, R.; Gallego, S.; Márquez, A.; Francés, J.; Martínez, F. J.; Pascual, I.; Beléndez, A.

2018-02-01

Holographic polymer dispersed liquid crystals (HPDLCs) are the result of the optimization of the photopolymer fabrication techniques. They are made by recording in a photopolymerization induced phase separation process (PIPS) in which the liquid crystal molecules diffuse to dark zones in the diffraction grating originated. Thanks to the addition of liquid crystal molecules to the composition, this material has a dynamic behavior by reorientation of the liquid crystal molecules applying an electrical field. In this sense, it is possible to use this material to make dynamic devices. In this work, we study the behavior of this material working in low frequencies with different spatial periods of blazed gratings, a sharp profile whose recording is possible thanks to the addition of a Holoeye LCoS-Pluto spatial light modulator with a resolution of 1920 × 1080 pixels (HD) and a pixel size of 8 × 8 μm2. This device allows us to have an accurate and dynamic control of the phase and amplitude of the recording beam.

Assessment of strobilurin fungicides' content in soya-based drinks by liquid micro-extraction and liquid chromatography with tandem mass spectrometry.

PubMed

Campillo, Natalia; Iniesta, María Jesús; Viñas, Pilar; Hernández-Córdoba, Manuel

2015-01-01

Seven strobilurin fungicides were pre-concentrated from soya-based drinks using dispersive liquid-liquid micro-extraction (DLLME) with a prior protein precipitation step in acid medium. The enriched phase was analysed by liquid chromatography (LC) with dual detection, using diode array detection (DAD) and electrospray-ion trap tandem mass spectrometry (ESI-IT-MS/MS). After selecting 1-undecanol and methanol as the extractant and disperser solvents, respectively, for DLLME, the Taguchi experimental method, an orthogonal array design, was applied to select the optimal solvent volumes and salt concentration in the aqueous phase. The matrix effect was evaluated and quantification was carried out using external aqueous calibration for DAD and matrix-matched calibration method for MS/MS. Detection limits in the 4-130 and 0.8-4.5 ng g(-1) ranges were obtained for DAD and MS/MS, respectively. The DLLME-LC-DAD-MS method was applied to the analysis of 10 different samples, none of which was found to contain residues of the studied fungicides.

Optimized method for the determination of itopride in human plasma by high-performance liquid chromatography with fluorimetric detection.

PubMed

Ptácek, Pavel; Klíma, Josef; Macek, Jan

2009-03-15

A high-performance liquid chromatographic method with fluorescence detection for the determination of itopride in human plasma is reported. The sample preparation was based on liquid-liquid extraction of itopride from plasma with t-butylmethylether and dichloromethane (70:30, v/v) mixture followed by a back extraction of the analyte to the phosphate buffer (pH 3.2). Liquid chromatography was performed on an octadecylsilica column (55 mm x 4 mm, 3 microm particles), the mobile phase consisted of acetonitrile-triethylamine-15 mM dihydrogenpotassium phosphate (14.5:0.5:85, v/v/v), pH of the mobile phase was adjusted to 4.8. The run time was 3 min. The fluorimetric detector was operated at 250/342 nm (excitation/emission wavelength). Naratriptan was used as the internal standard. The limit of quantitation was 9.5 ng/ml using 0.5 ml of plasma. The method precision and inaccuracy were less than 8%. The assay was applied to the analysis of samples from a bioequivalence study.

Quantitative analysis of psilocybin and psilocin in psilocybe baeocystis (Singer and Smith) by high-performance liquid chromatography and by thin-layer chromatography.

PubMed

Beug, M W; Bigwood, J

1981-03-27

Rapid quantification of psilocybin and psilocin in extracts of wild mushrooms is accomplished by reversed-phase high-performance liquid chromatography with paired-ion reagents. Nine solvent systems and three solid supports are evaluated for their efficiency in separating psilocybin, psilocin and other components of crude mushroom extracts by thin-layer chromatography.

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.

Ultra-high-pressure liquid chromatography-tandem mass spectrometry method for the determination of alkylphenols in soil.

PubMed

Wang, Jing; Pan, Hefang; Liu, Zhengzheng; Ge, Fei

2009-03-20

A novel method has been developed for the determination of alkylphenols in soil by ultra-high-pressure liquid chromatography employing small particle sizes, combined with tandem mass spectrometry. Soil samples were extracted with pressurized liquid extraction (PLE) and then cleaned with solid-phase extraction (SPE). The extracts were separated on C18 column (1.7 microm, 50 mm x 2.1mm) with a gradient elution and a mobile phase consisting of water and acetonitrile, and then detected by an electrospray ionization tandem mass spectrometry in negative ion mode with multiple reaction monitoring (MRM). Compared with traditional liquid chromatography, it took ultra-high-pressure liquid chromatography much less time to analyze alkylphenols. Additionally, the ultra-high-pressure liquid chromatography/tandem mass spectrometry method produces satisfactory reliability, sensitivity, and accuracy. The average recoveries of the three target analytes were 74.0-103.4%, with the RSD<15%. The calibration curves for alkylphenols were linear within the range of 0.01-0.4 microg/ml, with the correlation coefficients greater than 0.99. When 10 g soil sample was used for analysis, the limits of quantification (LOQs) of the three alkylphenols were all 1.0 microg/kg.

Polarity-based fractionation in proteomics: hydrophilic interaction vs reversed-phase liquid chromatography.

PubMed

Jafari, M; Mirzaie, M; Khodabandeh, M; Rezadoost, H; Ghassempour, A; Aboul-Enein, H Y

2016-07-01

During recent decades, hydrophilic interaction liquid chromatography (HILIC) ahs been introduced to fractionate or purify especially polar solutes such as peptides and proteins while reversed-phase liquid chromatography (RPLC) is also a common strategy. RPLC is also a common dimension in multidimensional chromatography. In this study, the potential of HILIC vs RPLC chromatography was compared for proteome mapping of human peripheral blood mononuclear cell extract. In HILIC a silica-based stationary phase and for RPLC a C18 column were applied. Then separated proteins were eluted to an ion trap mass spectrometry system. Our results showed that the HILIC leads to more proteins being identified in comparison to RPLC. Among the total 181 identified proteins, 56 and 38 proteins were fractionated specifically by HILIC and RPLC, respectively. In order to demonstrate this, the physicochemical properties of identified proteins such as polarity and hydrophobicity were considered. This analysis indicated that polarity may play a major role in the HILIC separation of proteins vs RPLC. Using gene ontology enrichment analysis, it was also observed that differences in physicochemical properties conform to the cellular compartment and biological features. Finally, this study highlighted the potential of HILIC and the great orthogonality of RPLC in gel-free proteomic studies. Copyright © 2015 John Wiley & Sons, Ltd. Copyright © 2015 John Wiley & Sons, Ltd.

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.

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

NASA Technical Reports Server (NTRS)

Elliott, D. G. (Inventor)

1979-01-01

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

Sensitive determination of nitrophenol isomers by reverse-phase high-performance liquid chromatography in conjunction with liquid-liquid extraction

USDA-ARS?s Scientific Manuscript database

A method for the highly sensitive determination of 2-, 3- and 4- nitrophenols was developed using reverse-phase high-performance liquid chromatography (RP-HPLC) with a UV photodiode array detector. Using a reverse-phase column and 40% aqueous acetonitrile as an eluent (i.e. isocratic elution), the i...

Analytical methods for the assessment of endocrine disrupting chemical exposure during human fetal and lactation stages: a review.

PubMed

Jiménez-Díaz, I; Vela-Soria, F; Rodríguez-Gómez, R; Zafra-Gómez, A; Ballesteros, O; Navalón, A

2015-09-10

In the present work, a review of the analytical methods developed in the last 15 years for the determination of endocrine disrupting chemicals (EDCs) in human samples related with children, including placenta, cord blood, amniotic fluid, maternal blood, maternal urine and breast milk, is proposed. Children are highly vulnerable to toxic chemicals in the environment. Among these environmental contaminants to which children are at risk of exposure are EDCs -substances able to alter the normal hormone function of wildlife and humans-. The work focuses mainly on sample preparation and instrumental techniques used for the detection and quantification of the analytes. The sample preparation techniques include, not only liquid-liquid extraction (LLE) and solid-phase extraction (SPE), but also modern microextraction techniques such as extraction with molecular imprinted polymers (MIPs), stir-bar sorptive extraction (SBSE), hollow-fiber liquid-phase microextraction (HF-LPME), dispersive liquid-liquid microextraction (DLLME), matrix solid phase dispersion (MSPD) or ultrasound-assisted extraction (UAE), which are becoming alternatives in the analysis of human samples. Most studies focus on minimizing the number of steps and using the lowest solvent amounts in the sample treatment. The usual instrumental techniques employed include liquid chromatography (LC), gas chromatography (GC) mainly coupled to tandem mass spectrometry. Multiresidue methods are being developed for the determination of several families of EDCs with one extraction step and limited sample preparation. Copyright © 2015 Elsevier B.V. All rights reserved.

A polyacrylamide-based silica stationary phase for the separation of carbohydrates using alcohols as the weak eluent in hydrophilic interaction liquid chromatography.

PubMed

Cai, Jianfeng; Cheng, Lingping; Zhao, Jianchao; Fu, Qing; Jin, Yu; Ke, Yanxiong; Liang, Xinmiao

2017-11-17

A hydrophilic interaction liquid chromatography (HILIC) stationary phase was prepared by a two-step synthesis method, immobilizing polyacrylamide on silica sphere particles. The stationary phase (named PA, 5μm dia) was evaluated using a mixture of carbohydrates in HILIC mode and the column efficiency reached 121,000Nm -1 . The retention behavior of carbohydrates on PA stationary phase was investigated with three different organic solvents (acetonitrile, ethanol and methanol) employed as the weak eluent. The strongest hydrophilicity of PA stationary phase was observed in both acetonitrile and methanol as the weak eluent, when compared with another two amide stationary phases. Attributing to its high hydrophilicity, three oligosaccharides (xylooligosaccharide, fructooligosaccharide and chitooligosaccharides) presented good retention on PA stationary phase using alcohols/water as mobile phase. Finally, PA stationary phase was successfully applied for the purification of galactooligosaccharides and saponins of Paris polyphylla. It is feasible to use safer and cheaper alcohols to replace acetonitrile as the weak eluent for green analysis and purification of polar compounds on PA stationary phase. Copyright © 2017. Published by Elsevier B.V.

Application of ionic liquid in liquid phase microextraction technology.

PubMed

Han, Dandan; Tang, Baokun; Lee, Yu Ri; Row, Kyung Ho

2012-11-01

Ionic liquids (ILs) are novel nonmolecular solvents. Their unique properties, such as high thermal stability, tunable viscosity, negligible vapor pressure, nonflammability, and good solubility for inorganic and organic compounds, make them excellent candidates as extraction media for a range of microextraction techniques. Many physical properties of ILs can be varied, and the structural design can be tuned to impart the desired functionality and enhance the analyte extraction selectivity, efficiency, and sensitivity. This paper provides an overview of the applications of ILs in liquid phase microextraction technology, such as single-drop microextraction, hollow fiber based liquid phase microextraction, and dispersive liquid-liquid microextraction. The sensitivity, linear calibration range, and detection limits for a range of target analytes in the methods were analyzed to determine the advantages of ILs in liquid phase microextraction. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A Liquid Optical Phase Shifter with an Embedded Electrowetting Actuator

PubMed Central

Ashtiani, Alireza Ousati; Jiang, Hongrui

2017-01-01

We demonstrate an electrowetting-based liquid optical phase shifter. The phase shifter consists of two immiscible liquid layers with different refractive indices. Sandwiched between the two liquids is a rigid membrane that moves freely along the optical axis and supported by a compliant surround. When applied with a pressure, the thicknesses of both liquid layers change, which induces a difference in optical path, resulting in a phase shift. A miniaturized electrowetting-based actuator is used to produce hydraulic pressure. A multi-layered SU8 bonded structure was fabricated. A phase shift of 171° was observed when the device was incorporated in a Mach-Zehnder interferometer and driven with 100 V. PMID:29038640

Simultaneous determination of three purines in Alysicarpus vaginalis (L.) DC. by hollow fiber-based liquid-phase microextraction combined with high-performance liquid chromatography.

PubMed

Liu, Hongjiao; Lei, Ming; Liang, Xiao; Jiang, Zhen; Guo, Xingjie

2014-02-01

In this paper, a three-phase hollow fiber liquid-phase microextraction (HF-LPME) method combined with high-performance liquid chromatography (HPLC) was developed for the determination of hypoxanthine (HX), xanthine (Xan) and adenine (A) and then for the first time successfully applied to the analysis of HX, Xan and A in Alysicarpus vaginalis (L.) DC. medicinal materials. Different factors affecting the HF-LPME procedure were investigated and optimized. Under optimal extraction conditions (1-octanol as organic solvent, pH of the donor and acceptor phase 10.0 and 3.5, respectively, extraction time 40 min, stirring rate 800 rpm and salt addition 10%, w/v), HX, Xan and A could be determined within the test ranges with a good correlation coefficient (r(2) > 0.9992). The limit of detection for HX, Xan and A was 153, 173 and 97 ng/mL, respectively, and the intra- and inter-day relative standard deviations were no more than 9.8%. The content of HX, Xan and A in Alysicarpus vaginalis (L.) DC. medicinal materials was 120.40, 18.37 and 62.75 µg/g, respectively. This procedure afforded a convenient, sensitive, accurate and inexpensive method with a high extraction efficiency for determination of HX, Xan and A. Copyright © 2013 John Wiley & Sons, Ltd.

A Theoretical Study of Love Wave Sensors Based on ZnO–Glass Layered Structures for Application to Liquid Environments

PubMed Central

Caliendo, Cinzia; Hamidullah, Muhammad

2016-01-01

The propagation of surface acoustic Love modes along ZnO/glass-based structures was modeled and analysed with the goal of designing a sensor able to detect changes in the environmental parameters, such as liquid viscosity changes and minute amounts of mass supported in the viscous liquid medium. Love mode propagation was modeled by numerically solving the system of coupled electro-mechanical field equations and Navier–Stokes equations. The phase and group velocities and the attenuation of the acoustic wave propagating along the 30° tilted c-axis ZnO/glass structure contacting a viscous non-conductive liquid were calculated for different ZnO guiding layer thicknesses, added mass thicknesses, and liquid viscosity and density. The three sensor responses, i.e., the wave phase and group velocity, and attenuation changes are calculated for different environmental parameters and related to the sensor velocity and attenuation sensitivities. The resulted sensitivities to liquid viscosity and added mass were optimized by adjusting the ZnO guiding layer thickness corresponding to a sensitivity peak. The present analysis is valuable for the manufacture and application of the ZnO-glass structure Love wave sensors for the detection of liquid properties, such as viscosity, density and mass anchored to the sensor surface. PMID:27918419

Comparing the catalytic oxidation of ethanol at the solid-gas and solid-liquid interfaces over size-controlled Pt nanoparticles: striking differences in kinetics and mechanism.

PubMed

Sapi, Andras; Liu, Fudong; Cai, Xiaojun; Thompson, Christopher M; Wang, Hailiang; An, Kwangjin; Krier, James M; Somorjai, Gabor A

2014-11-12

Pt nanoparticles with controlled size (2, 4, and 6 nm) are synthesized and tested in ethanol oxidation by molecular oxygen at 60 °C to acetaldehyde and carbon dioxide both in the gas and liquid phases. The turnover frequency of the reaction is ∼80 times faster, and the activation energy is ∼5 times higher at the gas-solid interface compared to the liquid-solid interface. The catalytic activity is highly dependent on the size of the Pt nanoparticles; however, the selectivity is not size sensitive. Acetaldehyde is the main product in both media, while twice as much carbon dioxide was observed in the gas phase compared to the liquid phase. Added water boosts the reaction in the liquid phase; however, it acts as an inhibitor in the gas phase. The more water vapor was added, the more carbon dioxide was formed in the gas phase, while the selectivity was not affected by the concentration of the water in the liquid phase. The differences in the reaction kinetics of the solid-gas and solid-liquid interfaces can be attributed to the molecular orientation deviation of the ethanol molecules on the Pt surface in the gas and liquid phases as evidenced by sum frequency generation vibrational spectroscopy.

High Performance Liquid Chromatography

NASA Astrophysics Data System (ADS)

Talcott, Stephen

High performance liquid chromatography (HPLC) has many applications in food chemistry. Food components that have been analyzed with HPLC include organic acids, vitamins, amino acids, sugars, nitrosamines, certain pesticides, metabolites, fatty acids, aflatoxins, pigments, and certain food additives. Unlike gas chromatography, it is not necessary for the compound being analyzed to be volatile. It is necessary, however, for the compounds to have some solubility in the mobile phase. It is important that the solubilized samples for injection be free from all particulate matter, so centrifugation and filtration are common procedures. Also, solid-phase extraction is used commonly in sample preparation to remove interfering compounds from the sample matrix prior to HPLC analysis.

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.

Sensitive gas analysis system on a microchip and application for on-site monitoring of NH3 in a clean room.

PubMed

Hiki, Shinichiro; Mawatari, Kazuma; Aota, Arata; Saito, Maki; Kitamori, Takehiko

2011-06-15

A portable, highly sensitive, and continuous ammonia gas monitoring system was developed with a microfluidic chip. The system consists of a main unit, a gas pumping unit, and a computer which serves as an operation console. The size of the system is 45 cm width × 30 cm depth × 30 cm height, and the portable system was realized. A highly efficient and stable extraction method was developed by utilizing an annular gas/liquid laminar flow. In addition, a stable gas/liquid separation method with a PTFE membrane was developed by arranging a fluidic network in three dimensions to achieve almost zero dead volume at the gas/liquid extraction part. The extraction rate was almost 100% with a liquid flow rate of 3.5 μL/min and a gas flow rate of 100 mL/min (contact time of ~15 ms), and the concentration factor was 200 times by calculating the NH(3) concentration (w/w unit) in the gas and liquid phases. Stable phase separation and detection was sustained for more than 3 weeks in an automated operation, which was sufficient for the monitoring application. The lower limit of detection calculated based on a signal-to-noise ratio of 3 was 84 ppt, which showed good detectability for NH(3) analysis. We believe that our system is a very powerful tool for gas analysis due to the advantages of portable size, high sensitivity, and continuous monitoring, and it is particularly useful in the semiconductor field.

Effects of solvent density on retention in gas-liquid chromatography. I. Alkanes solutes in polyethylene glycol stationary phases.

PubMed

González, F R; Pérez-Parajón, J; García-Domínguez, J A

2002-04-12

Gas-liquid chromatographic columns were prepared coating silica capillaries with poly(oxyethylene) polymers of different molecular mass distributions, in the range of low number-average molar masses, where the density still varies significantly. A novel, high-temperature, rapid evaporation method was developed and applied to the static coating of the low-molecular-mass stationary phases. The analysis of alkanes retention data from these columns reveals that the dependence of the partition coefficient with the solvent macroscopic density is mainly due to a variation of entropy. Enthalpies of solute transfer contribute poorly to the observed variations of retention. Since the alkanes solubility diminishes with the increasing solvent density, and this variation is weakly dependent with temperature, it is concluded that the decrease of free-volume in the liquid is responsible for this behavior.

A finite element analysis of the freeze/thaw behavior of external artery heat pipes

NASA Technical Reports Server (NTRS)

Lu, X. J.; Peterson, G. P.

1993-01-01

A two-dimensional finite element model was used to determine the freeze/thaw characteristics of an external artery heat pipe. During startup, the working fluid, which was located in the liquid channel and the circumferential wall grooves, experienced a phase transformation from a solid to a liquid state. The transient heat conduction equations with moving interfacial conditions were solved using the appropriate initial boundary conditions. The modelling results include the cross-sectional temperature distribution and the interfacial or melt front position as a function of time. A fixed grid approach was adopted in the model for the phase-change process during thawing of frozen working fluid. The interfacial position between the liquid and solid regions was found by balancing the latent heat caused by interfacial movement with the heat addition or extraction at the related grid points.

Analytical instrument with apparatus and method for sample concentrating

DOEpatents

Zaromb, S.

1986-08-04

A system for analysis of trace concentrations of contaminants in air includes a portable liquid chromatograph and a preconcentrator for the contaminants to be analyzed. The preconcentrator includes a sample bag having an inlet valve and an outlet valve for collecting an air sample. When the sample is collected the sample bag is connected in series with a sorbing apparatus in a recirculation loop. The sorbing apparatus has an inner gas-permeable container containing a sorbent material and an outer gas-impermeable container. The sample is circulated through the outer container and around the inner container for trapping and preconcentrating the contaminants in the sorbent material. The sorbent material may be a liquid having the same composition as the mobile phase of the chromatograph for direct injection thereinto. Alternatively, the sorbent material may be a porous, solid body, to which mobile phase liquid is added after preconcentration of the contaminants for dissolving the contaminants, the liquid solution then being withdrawn for injection into the chromatograph.

Analytical instrument with apparatus for sample concentrating

DOEpatents

Zaromb, Solomon

1989-01-01

A system for analysis of trace concentrations of contaminants in air includes a portable liquid chromatograph and a preconcentrator for the contaminants to be analyzed. The preconcentrator includes a sample bag having an inlet valve and an outlet valve for collecting an air sample. When the sample is collected the sample bag is connected in series with a sorbing apparatus in a recirculation loop. The sorbing apparatus has an inner gas-permeable container containing a sorbent material and an outer gas-impermeable container. The sample is circulated through the outer container and around the inner container for trapping and preconcentrating the contaminants in the sorbent material. The sorbent material may be a liquid having the same composition as the mobile phase of the chromatograph for direct injection thereinto. Alternatively, the sorbent material may be a porous, solid body, to which mobile phase liquid is added after preconcentration of the contaminants for dissolving the contaminants, the liquid solution then being withdrawn for injection into the chromatograph.

Method and apparatus for the removal of bioconversion of constituents of organic liquids

DOEpatents

Scott, Timothy; Scott, Charles D.

1994-01-01

A method and apparatus for the removal or conversion of constituents from bulk organic liquids. A countercurrent biphasic bioreactor system is utilized to disperse and recoalesce a biocatalyst contained in the aqueous liquid phase into the organic liquid phase containing the constituent. Two transient, high-intensity electrical fields rupture the aqueous drops into a plurality of microdroplets and induce continuous coalescence and redispersion as the microdroplets travel through the organic phase, thus increasing surface area. As the aqueous microdroplets progress through the organic phase, the biocatalyst then reacts with the constituent to produce a product which is then removed from the bioreactor in the aqueous phase or retained in the organic phase. The organic liquid, now free of the original constituents, is ready for immediate use or further processing.

Liquid hyperpolarized 129Xe produced by phase exchange in a convection cell

NASA Astrophysics Data System (ADS)

Su, T.; Samuelson, G. L.; Morgan, S. W.; Laicher, G.; Saam, B.

2004-09-01

We present a method for the production of liquid hyperpolarized Xe129 that employs spin-exchange optical pumping in the gas phase and subsequent phase exchange with a column of xenon liquid. A convection loop inside the sealed glass cell allows efficient transfer of magnetization between the gas and liquid phases. By condensing to liquid a large fraction of the sample, this scheme permits the polarization of many more Xe129 atoms in a given sealed-cell volume than would otherwise be possible. We have thus far produced a steady-state polarization of 8% in 0.1mL of liquid with a characteristic rise time of ≈15min.

Developing the Pulsed Fission-Fusion (PuFF) Engine

NASA Technical Reports Server (NTRS)

Adams, Robert B.; Cassibry, Jason; Bradley, David; Fabisinski, Leo; Statham, Geoffrey

2014-01-01

In September 2013 the NASA Innovative Advanced Concept (NIAC) organization awarded a phase I contract to the PuFF team. Our phase 1 proposal researched a pulsed fission-fusion propulsion system that compressed a target of deuterium (D) and tritium (T) as a mixture in a column, surrounded concentrically by Uranium. The target is surrounded by liquid lithium. A high power current would flow down the liquid lithium and the resulting Lorentz force would compress the column by roughly a factor of 10. The compressed column would reach criticality and a combination of fission and fusion reactions would occur. Our Phase I results, summarized herein, review our estimates of engine and vehicle performance, our work to date to model the fission-fusion reaction, and our initial efforts in experimental analysis.

Rapid liquid phase sintered Mn doped BiFeO3 ceramics with enhanced polarization and weak magnetization

NASA Astrophysics Data System (ADS)

Kumar, Manoj; Yadav, K. L.

2007-12-01

Single-phase BiFe1-xMnxO3 multiferroic ceramics have been synthesized by rapid liquid phase sintering method to study the influence of Mn substitution on their crystal structure, dielectric, magnetic, and ferroelectric behaviors. From XRD analysis it is seen that Mn substitution does not affect the crystal structure of the BiFe1-xMnxO3 system. An enhancement in magnetization was observed for BiFe1-xMnxO3 ceramics. However, the ferooelectric hysteresis loops were not really saturated, we observed a spontaneous polarization of 10.23μC /cm2 under the applied field of 42kV/cm and remanent polarization of 3.99μC/cm2 for x =0.3 ceramic.

Flow-pattern identification and nonlinear dynamics of gas-liquid two-phase flow in complex networks.

PubMed

Gao, Zhongke; Jin, Ningde

2009-06-01

The identification of flow pattern is a basic and important issue in multiphase systems. Because of the complexity of phase interaction in gas-liquid two-phase flow, it is difficult to discern its flow pattern objectively. In this paper, we make a systematic study on the vertical upward gas-liquid two-phase flow using complex network. Three unique network construction methods are proposed to build three types of networks, i.e., flow pattern complex network (FPCN), fluid dynamic complex network (FDCN), and fluid structure complex network (FSCN). Through detecting the community structure of FPCN by the community-detection algorithm based on K -mean clustering, useful and interesting results are found which can be used for identifying five vertical upward gas-liquid two-phase flow patterns. To investigate the dynamic characteristics of gas-liquid two-phase flow, we construct 50 FDCNs under different flow conditions, and find that the power-law exponent and the network information entropy, which are sensitive to the flow pattern transition, can both characterize the nonlinear dynamics of gas-liquid two-phase flow. Furthermore, we construct FSCN and demonstrate how network statistic can be used to reveal the fluid structure of gas-liquid two-phase flow. In this paper, from a different perspective, we not only introduce complex network theory to the study of gas-liquid two-phase flow but also indicate that complex network may be a powerful tool for exploring nonlinear time series in practice.

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.

Surface thermodynamic analysis of fluid confined in a cone and comparison with the sphere-plate and plate-plate geometries.

PubMed

Zargarzadeh, Leila; Elliott, Janet A W

2013-10-22

The behavior of pure fluid confined in a cone is investigated using thermodynamic stability analysis. Four situations are explained on the basis of the initial confined phase (liquid/vapor) and its pressure (above/below the saturation pressure). Thermodynamic stability analysis (a plot of the free energy of the system versus the size of the new potential phase) reveals whether the phase transition is possible and, if so, the number and type (unstable/metastable/stable) of equilibrium states in each of these situations. Moreover we investigated the effect of the equilibrium contact angle and the cone angle (equivalent to the confinement's surface separation distance) on the free energy (potential equilibrium states). The results are then compared to our previous study of pure fluid confined in the gap between a sphere and a flat plate and the gap between two flat plates.1 Confined fluid behavior of the four possible situations (for these three geometries) can be explained in a unified framework under two categories based on only the meniscus shape (concave/convex). For systems with bulk-phase pressure imposed by a reservoir, the stable coexistence of pure liquid and vapor is possible only when the meniscus is concave.

Liquidus Diagram of the Ba-Y-Cu-O System in the Vicinity of the Ba2YCu3O6+x Phase Field

PubMed Central

Wong-Ng, Winnie; Cook, Lawrence P.

1998-01-01

This paper describes the melting equilibria in the vicinity of the high Tc phase Ba2YCu3O6+x, including evidence for two Ba-Y-Cu-O immiscible liquids. Melting equilibria have been investigated in purified air using a combination of differential thermal analysis (DTA), thermogravimetric analysis (TGA), powder x-ray diffraction (XRD), MgO wick entrapment of liquid for analysis, scanning electron microscopy (SEM) coupled with energy dispersive x-ray analysis (EDS), and hydrogen reduction for determination of copper oxidation state. For relatively barium-rich compositions, it was necessary to prepare the starting materials under controlled atmosphere conditions using BaO. A liquidus diagram was derived from quantitative data for the melts involved in various melting reactions. In general the 1/2(Y2O3) contents of the melts participating in these equilibria were low (mole fraction <4 %). The primary phase field of Ba2YCu3O6+x occurs at a mole fraction of <2.0 % 1/2Y2O3 and lies very close along the BaO-CuOx edge, extending from a mole fraction of ≈43 % CuO to a mole fraction of ≈76 % CuO. It is divided by a liquid miscibility gap and extends on either side about this gap. The topological sequence of melting reactions associated with the liquidus is presented as a function of temperature. Implications for the growth of Ba2YCu3O6+x crystals are discussed. PMID:28009382

Multicriteria decision analysis in ranking of analytical procedures for aldrin determination in water.

PubMed

Tobiszewski, Marek; Orłowski, Aleksander

2015-03-27

The study presents the possibility of multi-criteria decision analysis (MCDA) application when choosing analytical procedures with low environmental impact. A type of MCDA, Preference Ranking Organization Method for Enrichment Evaluations (PROMETHEE), was chosen as versatile tool that meets all the analytical chemists--decision makers requirements. Twenty five analytical procedures for aldrin determination in water samples (as an example) were selected as input alternatives to MCDA analysis. Nine different criteria describing the alternatives were chosen from different groups--metrological, economical and the most importantly--environmental impact. The weights for each criterion were obtained from questionnaires that were sent to experts, giving three different scenarios for MCDA results. The results of analysis show that PROMETHEE is very promising tool to choose the analytical procedure with respect to its greenness. The rankings for all three scenarios placed solid phase microextraction and liquid phase microextraction--based procedures high, while liquid-liquid extraction, solid phase extraction and stir bar sorptive extraction--based procedures were placed low in the ranking. The results show that although some of the experts do not intentionally choose green analytical chemistry procedures, their MCDA choice is in accordance with green chemistry principles. The PROMETHEE ranking results were compared with more widely accepted green analytical chemistry tools--NEMI and Eco-Scale. As PROMETHEE involved more different factors than NEMI, the assessment results were only weakly correlated. Oppositely, the results of Eco-Scale assessment were well-correlated as both methodologies involved similar criteria of assessment. Copyright © 2015 Elsevier B.V. All rights reserved.

Study on dynamic deformation synchronized measurement technology of double-layer liquid surfaces

NASA Astrophysics Data System (ADS)

Tang, Huiying; Dong, Huimin; Liu, Zhanwei

2017-11-01

Accurate measurement of the dynamic deformation of double-layer liquid surfaces plays an important role in many fields, such as fluid mechanics, biomechanics, petrochemical industry and aerospace engineering. It is difficult to measure dynamic deformation of double-layer liquid surfaces synchronously for traditional methods. In this paper, a novel and effective method for full-field static and dynamic deformation measurement of double-layer liquid surfaces has been developed, that is wavefront distortion of double-wavelength transmission light with geometric phase analysis (GPA) method. Double wavelength lattice patterns used here are produced by two techniques, one is by double wavelength laser, and the other is by liquid crystal display (LCD). The techniques combine the characteristics such as high transparency, low reflectivity and fluidity of liquid. Two color lattice patterns produced by laser and LCD were adjusted at a certain angle through the tested double-layer liquid surfaces simultaneously. On the basis of the refractive indexes difference of two transmitted lights, the double-layer liquid surfaces were decoupled with GPA method. Combined with the derived relationship between phase variation of transmission-lattice patterns and out-of plane heights of two surfaces, as well as considering the height curves of the liquid level, the double-layer liquid surfaces can be reconstructed successfully. Compared with the traditional measurement method, the developed method not only has the common advantages of the optical measurement methods, such as high-precision, full-field and non-contact, but also simple, low cost and easy to set up.

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...

The Particle Distribution in Liquid Metal with Ceramic Particles Mould Filling Process

NASA Astrophysics Data System (ADS)

Dong, Qi; Xing, Shu-ming

2017-09-01

Adding ceramic particles in the plate hammer is an effective method to increase the wear resistance of the hammer. The liquid phase method is based on the “with the flow of mixed liquid forging composite preparation of ZTA ceramic particle reinforced high chromium cast iron hammer. Preparation method for this system is using CFD simulation analysis the particles distribution of flow mixing and filling process. Taking the 30% volume fraction of ZTA ceramic composite of high chromium cast iron hammer as example, by changing the speed of liquid metal viscosity to control and make reasonable predictions of particles distribution before solidification.

Background Information on the He(3) Nuclear Gyroscope.

DTIC Science & Technology

1983-02-01

however, that sincew0 is not fixed by any constant of nature , its phase and frequency must be initially established by measurement when the gyro case is...sequence of longitudinal relaxation time (T1) measurements were made on a standard He3 -He4 liquid mixture (He3 concentration of 7 x 10 4) as a function of...Analysis of Experimental FPD Data on a Liquid Mixture Free precession data of a standard He 3-He4 liquid mixture (He3 concentration of 7 x 10- 4) were

Hollow porous ionic liquids composite polymers based solid phase extraction coupled online with high performance liquid chromatography for selective analysis of hydrophilic hydroxybenzoic acids from complex samples.

PubMed

Dai, Xingping; Wang, Dongsheng; Li, Hui; Chen, Yanyi; Gong, Zhicheng; Xiang, Haiyan; Shi, Shuyun; Chen, Xiaoqing

2017-02-10

Polar and hydrophilic properties of hydroxybenzoic acids usually made them coelute with interferences in high performance liquid chromatography (HPLC) analysis. Then selective analysis of them was necessary. Herein, hollow porous ionic liquids composite polymers (PILs) based solid phase extraction (SPE) was firstly fabricated and coupled online with HPLC for selective analysis of hydroxybenzoic acids from complex matrices. Hollow porous PILs were firstly synthesized using Mobil Composition of Matter No. 48 (MCM-48) spheres as sacrificial support, 1-vinyl-3-methylimidazolium chloride (VMIM + Cl - ) as monomer, and ethylene glycol dimethacrylate (EGDMA) as cross-linker. Various parameters affecting synthesis, adsorption and desorption behaviors were investigated and optimized. Steady-state adsorption studies showed the resulting hollow porous PILs exhibited high adsorption capacity, fast adsorption kinetics, and excellent specific adsorption. Subsequently, the application of online SPE system was studied by selective analysis of protocatechuic acid (PCA), 4-hydroxybenzoic acid (4-HBA), and vanillic acid (VA) from Pollen Typha angustifolia. The obtained limit of detection (LOD) varied from 0.002 to 0.01μg/mL, the linear range (0.05-5.0μg/mL) was wide with correlation coefficient (R) from 0.9982 to 0.9994, and the average recoveries at three spiking levels ranged from 82.7 to 102.4%, with column-to-column relative standard deviation (RSD) below 8.1%. The proposed online method showed good accuracy, precision, specificity and convenience, which opened up a universal and efficient route for selective analysis of hydroxybenzoic acids from complex samples. Copyright © 2017 Elsevier B.V. All rights reserved.

Rapid determination of triclosan in personal care products using new in-tube based ultrasound-assisted salt-induced liquid-liquid microextraction coupled with high performance liquid chromatography-ultraviolet detection.

PubMed

Chen, Ming-Jen; Liu, Ya-Ting; Lin, Chiao-Wen; Ponnusamy, Vinoth Kumar; Jen, Jen-Fon

2013-03-12

This paper describes the development of a novel, simple and efficient in-tube based ultrasound-assisted salt-induced liquid-liquid microextraction (IT-USA-SI-LLME) technique for the rapid determination of triclosan (TCS) in personal care products by high performance liquid chromatography-ultraviolet (HPLC-UV) detection. IT-USA-SI-LLME method is based on the rapid phase separation of water-miscible organic solvent from the aqueous phase in the presence of high concentration of salt (salting-out phenomena) under ultrasonication. In the present work, an indigenously fabricated home-made glass extraction device (8-mL glass tube inbuilt with a self-scaled capillary tip) was utilized as the phase separation device for USA-SI-LLME. After the extraction, the upper extractant layer was narrowed into the self-scaled capillary tip by pushing the plunger plug; thus, the collection and measurement of the upper organic solvent layer was simple and convenient. The effects of various parameters on the extraction efficiency were thoroughly evaluated and optimized. Under optimal conditions, detection was linear in the concentration range of 0.4-100ngmL(-1) with correlation coefficient of 0.9968. The limit of detection was 0.09ngmL(-1) and the relative standard deviations ranged between 0.8 and 5.3% (n=5). The applicability of the developed method was demonstrated for the analysis of TCS in different commercial personal care products and the relative recoveries ranged from 90.4 to 98.5%. The present method was proven to be a simple, sensitive, less organic solvent consuming, inexpensive and rapid procedure for analysis of TCS in a variety of commercially available personal care products or cosmetic preparations. Copyright © 2013 Elsevier B.V. All rights reserved.

Topological spinon bands and vison excitations in spin-orbit coupled quantum spin liquids

NASA Astrophysics Data System (ADS)

Sonnenschein, Jonas; Reuther, Johannes

2017-12-01

Spin liquids are exotic quantum states characterized by the existence of fractional and deconfined quasiparticle excitations, referred to as spinons and visons. Their fractional nature establishes topological properties such as a protected ground-state degeneracy. This work investigates spin-orbit coupled spin liquids where, additionally, topology enters via nontrivial band structures of the spinons. We revisit the Z2 spin-liquid phases that have recently been identified in a projective symmetry-group analysis on the square lattice when spin-rotation symmetry is maximally lifted [J. Reuther et al., Phys. Rev. B 90, 174417 (2014), 10.1103/PhysRevB.90.174417]. We find that in the case of nearest-neighbor couplings only, Z2 spin liquids on the square lattice always exhibit trivial spinon bands. Adding second-neighbor terms, the simplest projective symmetry-group solution closely resembles the Bernevig-Hughes-Zhang model for topological insulators. Assuming that the emergent gauge fields are static, we investigate vison excitations, which we confirm to be deconfined in all investigated spin phases. Particularly, if the spinon bands are topological, the spinons and visons form bound states consisting of several spinon-Majorana zero modes coupling to one vison. The existence of such zero modes follows from an exact mapping between these spin phases and topological p +i p superconductors with vortices. We propose experimental probes to detect such states in real materials.

Optical isotropy and iridescence in a smectic 'blue phase'.

PubMed

Yamamoto, Jun; Nishiyama, Isa; Inoue, Miyoshi; Yokoyama, Hiroshi

2005-09-22

When liquid crystal molecules are chiral, the twisted structure competes with spatially uniform liquid crystalline orders, resulting in a variety of modulated liquid crystal phases, such as the cholesteric blue phase, twist grain boundary and smectic blue phases. Here we report a liquid crystal smectic blue phase (SmBP(iso)), formed from a two-component mixture containing a chiral monomer and a 'twin' containing two repeat units of the first molecule connected by a linear hydrocarbon spacer. The phase exhibits the simultaneous presence of finite local-order parameters of helices and smectic layers, without any discontinuity on a mesoscopic length scale. The anomalous softening of elasticity due to a strong reduction in entropy caused by mixing the monomer and the twin permits the seamless coexistence of these two competing liquid crystal orders. The new phase spontaneously exhibits an optically isotropic but uniformly iridescent colour and automatically acquires spherical symmetry, so that the associated photonic band gap maintains the same symmetry despite the local liquid crystalline order. We expect a range of unusual optical transmission properties based on this three-dimensional isotropic structure, and complete tunability due to the intrinsic softness and responsiveness of the liquid crystalline order against external fields.

Pressure Induced Liquid-to-Liquid Transition in Zr-based Supercooled Melts and Pressure Quenched Glasses

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

Dmowski, W.; Gierlotka, S.; Wang, Z.

Through high-energy x-ray diffraction and atomic pair density function analysis we find that Zr-based metallic alloy, heated to the supercooled liquid state under hydrostatic pressure and then quenched to room temperature, exhibits a distinct glassy structure. The PDF indicates that the Zr-Zr distances in this glass are significantly reduced compared to those quenched without pressure. Annealing at the glass transition temperature at ambient pressure reverses structural changes and the initial glassy state is recovered. This result suggests that pressure causes a liquid-to-liquid phase transition in this metallic alloy supercooled melt. Such a pressure induced transition is known for covalent liquids,more » but has not been observed for metallic liquids. The High Pressure Quenched glasses are stable in ambient conditions after decompression.« less

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.

As-Cast Icosashedral Quasicrystals in Ti-Zr-Ni Alloys

NASA Astrophysics Data System (ADS)

Lee, Geun Woo; Gangopadhyay, Anup K.; Kelton, Kenneth F.

2002-03-01

Most Ti-based icosahedral quasicrystals (i-phase) obtained by rapid quenching from the melt are metastable and disordered. In contrast, the Ti-Zr-Ni i-phase prepared by low temperature annealing is stable and better ordered. This i-phase is formed by a solid-state transformation from C14 Laves phase and α (Ti/Zr) solid-solution phase. It has not been possible previously to grow this i-phase directly from the liquid. Here, the nucleation and growth of the i-phase from the liquid in as-cast Ti-Zr-Ni alloys is reported. Pentagonal growth ledges in as-cast Ti-Zr-Ni ingots are clearly observed. Transmission electron microscopy and x-ray diffraction studies confirm the phase identity. Differential scanning calorimetry measurements show an endothermic transformation from the i-phase to a phase mixture of the C14 Laves and solid-solution phases, demonstrating that this i-phase is also stable. The short time that the liquid remains in the Laves phase-forming-field and the higher nucleation rate of the i-phase, owing to the presumed similarity between the local atomic structures of the i-phase and liquid, allows the i-phase to nucleate and grow directly from the liquid. Container-less solidification studies using electrostatic levitation (ESL) techniques support this conclusion.

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

Selectivity optimization in green chromatography by gradient stationary phase optimized selectivity liquid chromatography.

PubMed

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

2010-11-12

Stationary phase optimized selectivity liquid chromatography (SOSLC) is a promising technique to optimize the selectivity of a given separation by using a combination of different stationary phases. Previous work has shown that SOSLC offers excellent possibilities for method development, especially after the recent modification towards linear gradient SOSLC. The present work is aimed at developing and extending the SOSLC approach towards selectivity optimization and method development for green chromatography. Contrary to current LC practices, a green mobile phase (water/ethanol/formic acid) is hereby preselected and the composition of the stationary phase is optimized under a given gradient profile to obtain baseline resolution of all target solutes in the shortest possible analysis time. With the algorithm adapted to the high viscosity property of ethanol, the principle is illustrated with a fast, full baseline resolution for a randomly selected mixture composed of sulphonamides, xanthine alkaloids and steroids. Copyright © 2010 Elsevier B.V. All rights reserved.

Thermally-actuated, phase change flow control for microfluidic systems.

PubMed

Chen, Zongyuan; Wang, Jing; Qian, Shizhi; Bau, Haim H

2005-11-01

An easy to implement, thermally-actuated, noninvasive method for flow control in microfluidic devices is described. This technique takes advantage of the phase change of the working liquid itself-the freezing and melting of a portion of a liquid slug-to noninvasively close and open flow passages (referred to as a phase change valve). The valve was designed for use in a miniature diagnostic system for detecting pathogens in oral fluids at the point of care. The paper describes the modeling, construction, and characteristics of the valve. The experimental results favorably agree with theoretical predictions. In addition, the paper demonstrates the use of the phase change valves for flow control, sample metering and distribution into multiple analysis paths, sealing of a polymerase chain reaction (PCR) chamber, and sample introduction into and withdrawal from a closed loop. The phase change valve is electronically addressable, does not require any moving parts, introduces only minimal dead volume, is leakage and contamination free, and is biocompatible.

Enhanced dual-frequency operation of a polymerized liquid crystal microplate by liquid crystal infiltration

NASA Astrophysics Data System (ADS)

Kumagai, Takayuki; Yoshida, Hiroyuki; Ozaki, Masanori

2017-04-01

The electric-field-induced switching behavior of a polymer microplate is investigated. A microplate fabricated with a photopolymerizable dual-frequency liquid crystal was surrounded by an unpolymerized photopolymerizable dual-frequency liquid crystal in the isotropic phase. As an electric field was applied along the plane of the microplate, the microplate switched to set its interior molecular orientation to be either parallel or perpendicular to the field, depending on the frequency. Analysis of the rotational behavior, as well as numerical calculations, showed that the surrounding unpolymerized photopolymerizable dual-frequency liquid crystal infiltrated into the microplate, which enhanced the dielectric properties of the microplate. To the best of our knowledge, this is the first report of an enhanced dual-frequency dielectric response of a polymer microplate induced by liquid crystal infiltration.

Development of a perfusion reversed-phase high performance liquid chromatography method for the characterisation of maize products using multivariate analysis.

PubMed

Rodriguez-Nogales, J M; Garcia, M C; Marina, M L

2006-02-03

A perfusion reversed-phase high performance liquid chromatography (RP-HPLC) method has been designed to allow rapid (3.4 min) separations of maize proteins with high resolution. Several factors, such as extraction conditions, temperature, detection wavelength and type and concentration of ion-pairing agent were optimised. A fine optimisation of the gradient elution was also performed by applying experimental design. Commercial maize products for human consumption (flours, precocked flours, fried snacks and extruded snacks) were characterised for the first time by perfusion RP-HPLC and their chromatographic profiles allowed a differentiation among products relating the different technological process used for their preparation. Furthermore, applying discriminant analysis makes it possible to group the samples according with the technological process suffered by maize products, obtaining a good prediction in 92% of the samples.

Analysis of Alpha Backgrounds in DarkSide-50

NASA Astrophysics Data System (ADS)

Monte, Alissa; DarkSide Collaboration

2017-01-01

DarkSide-50 is the current phase of the DarkSide direct dark matter search program, operating underground at the Laboratori Nazionali del Gran Sasso in Italy. The detector is a dual-phase argon Time Projection Chamber (TPC), designed for direct detection of Weakly Interacting Massive Particles, and housed within an active veto system of liquid scintillator and water Cherenkov detectors. Since switching to a target of low radioactivity argon extracted from underground sources in April, 2016, the background is no longer dominated by naturally occurring 39Ar. However, alpha backgrounds from radon and its daughters remain, both from the liquid argon bulk and internal detector surfaces. I will present details of the analysis used to understand and quantify alpha backgrounds, as well as to understand other types of radon contamination that may be present, and our sensitivity to them.

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.

Dispersed bubble reactor for enhanced gas-liquid-solids contact and mass transfer

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

Vimalchand, Pannalal; Liu, Guohai; Peng, WanWang

An apparatus to promote gas-liquid contact and facilitate enhanced mass transfer. The dispersed bubble reactor (DBR) operates in the dispersed bubble flow regime to selectively absorb gas phase constituents into the liquid phase. The dispersion is achieved by shearing the large inlet gas bubbles into fine bubbles with circulating liquid and additional pumped liquid solvent when necessary. The DBR is capable of handling precipitates that may form during absorption or fine catalysts that may be necessary to promote liquid phase reactions. The DBR can be configured with multistage counter current flow sections by inserting concentric cylindrical sections into the risermore » to facilitate annular flow. While the DBR can absorb CO.sub.2 in liquid solvents that may lead to precipitates at high loadings, it is equally capable of handling many different types of chemical processes involving solids (precipitates/catalysts) along with gas and liquid phases.« less

Quantitative Analysis of Aloins and Aloin-Emodin in Aloe Vera Raw Materials and Finished Products Using High-Performance Liquid Chromatography: Single-Laboratory Validation, First Action 2016.09.

PubMed

Kline, David; Ritruthai, Vicha; Babajanian, Silva; Gao, Quanyin; Ingle, Prashant; Chang, Peter; Swanson, Gary

2017-05-01

A single-laboratory validation study is described for a method of quantitative analysis of aloins (aloins A and B) and aloe-emodin in aloe vera raw materials and finished products. This method used HPLC coupled with UV detection at 380 nm for the aloins and 430 nm for aloe-emodin. The advantage of this test method is that the target analytes are concentrated from the sample matrix (either liquid or solid form) using stepwise liquid-liquid extraction (water-ethyl acetate-methanol), followed by solvent evaporation and reconstitution. This sample preparation process is suitable for different forms of products. The concentrating step for aloins and aloe-emodin has enhanced the method quantitation level to 20 parts per billion (ppb). Reversed-phase chromatography using a 250 × 4.6 mm column under gradient elution conditions was used. Mobile phase A is 0.1% acetic acid in water and mobile phase B is 0.1% acetic acid in acetonitrile. The HPLC run starts with a 20% mobile phase B that reaches 35% at 13 min. From 13 to 30 min, mobile phase B is increased from 35 to 100%. From 30 to 40 min, mobile phase B is changed from 100% back to the initial condition of 20% for re-equilibration. The flow rate is 1 mL/min, with a 100 μL injection volume. Baseline separation (Rs > 2.0) for aloins A and B and aloe-emodin was observed under this chromatographic condition. This test method was validated with raw materials of aloe vera 5× (liquid) and aloe vera 200× (powder) and finished products of aloe concentrate (liquid) and aloe (powder). The linearity of the method was studied from 10 to 500 ppb for aloins A and B and aloe-emodin, with correlation coefficients of 0.999964, 0.999957, and 0.999980, respectively. The test method was proven to be specific, precise, accurate, rugged, and suitable for the intended quantitative analysis of aloins and aloe-emodin in raw materials and finished products. The S/N for aloins A and B and aloe-emodin at 10 ppb level were 12, 10, and 8, respectively, indicating our conservative LOD level at 10 ppb (the typical LOD level S/N is about 3). The S/N for aloins A and B and aloe-emodin at the 20 ppb level were 17, 14, and 16, respectively, indicating our conservative LOQ level at 20 ppb (the typical LOQ level S/N is about 10). The stock standard solution of a mixture of aloins and aloe-emodin and a working standard solution were found to be stable for at least 19 days when stored refrigerated at 2-8°C, with a recovery of 100 ± 5%.

Nanosecond Pulsed Discharge in Water without Bubbles: A Fundamental Study of Initiation, Propagation and Plasma Characteristics

NASA Astrophysics Data System (ADS)

Seepersad, Yohan

The state of plasma is widely known as a gas-phase phenomenon, but plasma in liquids have also received significant attention over the last century. Generating plasma in liquids however is theoretically challenging, and this problem is often overcome via liquid-gas phase transition preceding the actual plasma formation. In this sense, plasma forms in gas bubbles in the liquid. Recent work at the Drexel Plasma Institute has shown that nanosecond pulsed electric fields can initiate plasma in liquids without any initial cavitation phase, at voltages below theoretical direct-ionization thresholds. This unique regime is poorly understood and does not fit into any current descriptive mechanisms. As with all new phenomena, a complete fundamental description is paramount to understanding its usefulness to practical applications. The primary goals of this research were to qualitatively and quantitatively understand the phenomenon of nanosecond pulsed discharge in liquids as a means to characterizing properties that may open up niche application possibilities. Analysis of the plasma was based on experimental results from non-invasive, sub-nanosecond time-resolved optical diagnostics, including direct imaging, transmission imaging (Schlieren and shadow), and optical emission spectroscopy. The physical characteristics of the plasma were studied as a function of variations in the electric field amplitude and polarity, liquid permittivity, and pulse duration. It was found that the plasma size and emission intensity was dependent on the permittivity of the liquid, as well as the voltage polarity, and the structure and dynamics were explained by a 'cold-lightning' mechanism. The under-breakdown dynamics at the liquid-electrode interface were investigated by transmission imaging to provide evidence for a novel mechanism for initiation based on the electrostriction. This mechanism was proposed by collaborators on the project and developed alongside the experimental work in this research. Finally, analysis of emission spectra obtained from the OH(A-X) band at 308 nm by the excited hydroxyl radical was performed to quantify the temperature parameters of the plasma. Boltzmann analysis was performed to quantify the rotational temperature of OH which correlates well to the liquid temperature, and Stark broadening of the ionic lines belonging to hydrogen and oxygen was analysed to estimate electron temperature. It was found that the liquid temperature remained close to bulk temperature with T_(n,i)<500 K, and that the electron temperature was very high Te˜6-10 eV. Finally, based on the characterization of the plasma parameters, several potential avenues for applications of this regime of plasma will be suggested. The complex physical and chemical dynamics established when plasma is generated within a liquid medium has unlocked new and fascinating possibilities in the areas of biomedicine, water treatment, material synthesis and nanoscience. The high density, low temperature plasma formed could potentially be harnessed to unlock new applications across these fields and more.

Vapor-Phase Infrared Absorptivity Coefficient of HN1

DTIC Science & Technology

2013-08-01

the boil-off of a bulk liquid nitrogen tank, across an alumina Soxhlet thimble in a glass holder filled with the analyte. A vapor–liquid...with mass spectrometry (MS) yielded the results shown in Table 3. Table 3. Results from Analysis of HN1 Sample Used for Determination of...2 yields (3) Equation 3 can then be solved at each frequency using a least-squares approach. This was

Method and apparatus for the removal or bioconversion of constituents of organic liquids

DOEpatents

Scott, T.; Scott, C.D.

1994-10-25

A method and apparatus are disclosed for the removal or conversion of constituents from bulk organic liquids. A countercurrent biphasic bioreactor system is utilized to disperse and recoalesce a biocatalyst contained in the aqueous liquid phase into the organic liquid phase containing the constituent. Two transient, high-intensity electrical fields rupture the aqueous drops into a plurality of microdroplets and induce continuous coalescence and redispersion as the microdroplets travel through the organic phase, thus increasing surface area. As the aqueous microdroplets progress through the organic phase, the biocatalyst then reacts with the constituent to produce a product which is then removed from the bioreactor in the aqueous phase or retained in the organic phase. The organic liquid, now free of the original constituents, is ready for immediate use or further processing. 1 fig.

Gas-Liquid Processing in Microchannels

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

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

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

HPTAM, a two-dimensional Heat Pipe Transient Analysis Model, including the startup from a frozen state

NASA Technical Reports Server (NTRS)

Tournier, Jean-Michel; El-Genk, Mohamed S.

1995-01-01

A two-dimensional Heat Pipe Transient Analysis Model, 'HPTAM,' was developed to simulate the transient operation of fully-thawed heat pipes and the startup of heat pipes from a frozen state. The model incorporates: (a) sublimation and resolidification of working fluid; (b) melting and freezing of the working fluid in the porous wick; (c) evaporation of thawed working fluid and condensation as a thin liquid film on a frozen substrate; (d) free-molecule, transition, and continuum vapor flow regimes, using the Dusty Gas Model; (e) liquid flow and heat transfer in the porous wick; and (f) thermal and hydrodynamic couplings of phases at their respective interfaces. HPTAM predicts the radius of curvature of the liquid meniscus at the liquid-vapor interface and the radial location of the working fluid level (liquid or solid) in the wick. It also includes the transverse momentum jump condition (capillary relationship of Pascal) at the liquid-vapor interface and geometrically relates the radius of curvature of the liquid meniscus to the volume fraction of vapor in the wick. The present model predicts the capillary limit and partial liquid recess (dryout) in the evaporator wick, and incorporates a liquid pooling submodel, which simulates accumulation of the excess liquid in the vapor core at the condenser end.

Ionic liquid phases with comprehensive two-dimensional gas chromatography of fatty acid methyl esters.

PubMed

Pojjanapornpun, Siriluck; Nolvachai, Yada; Aryusuk, Kornkanok; Kulsing, Chadin; Krisnangkura, Kanit; Marriott, Philip J

2018-02-17

New generation inert ionic liquid (iIL) GC columns IL60i, IL76i and IL111i, comprising phosphonium or imidazolium cationic species, were investigated for separation of fatty acid methyl esters (FAME). In general, the iIL phases provide comparable retention times to their corresponding conventional columns, with only minor selectivity differences. The average tailing factors and peak widths were noticeably improved (reduced) for IL60i and IL76i, while they were slightly improved for IL111i. Inert IL phase columns were coupled with conventional IL columns in comprehensive two-dimensional GC (GC × GC) with a solid-state modulator which offers variable modulation temperature (T M ), programmable T M during analysis and trapping stationary phase material during the trap/release (modulation) process, independent of oven T and column sets. Although IL phases are classified as polar, relative polarity of the two phases comprising individual GC × GC column sets permits combination of less-polar IL/polar IL and polar IL/less-polar IL column sets; it was observed that a polar/less-polar column set provided better separation of FAME. A higher first dimension ( 1 D) phase polarity combined with a lower 2 D phase polarity, for instance 1 D IL111i with 2 D IL59 gave the best result; the greater difference in 1 D/ 2 D phase polarity results in increasing occupancy of peak area in the 2D space. The IL111i/IL59 column set was selected for analysis of fatty acids in fat and oil products (butter, margarine, fish oil and canola oil). Compared with the conventional IL111, IL111i showed reduced column bleed which makes this more suited to GC × GC analysis of FAME. The proposed method offers a fast profiling approach with good repeatability of analysis of FAME.

Development of continuous dispersive liquid-liquid microextraction performed in home-made device for extraction and preconcentration of aryloxyphenoxy-propionate herbicides from aqueous samples followed by gas chromatography-flame ionization detection.

PubMed

Farajzadeh, Mir Ali; Mohebbi, Ali; Feriduni, Behruz

2016-05-12

In this study, a rapid, simple, and efficient sample preparation method based on continuous dispersive liquid-liquid microextraction has been developed for the extraction and preconcentration of aryloxyphenoxy-propionate herbicides from aqueous samples prior to their analysis by gas chromatography-flame ionization detection. In this method, two parallel glass tubes with different diameters are connected with a teflon stopcock and used as an extraction device. A mixture of disperser and extraction solvents is transferred into one side (narrow tube) of the extraction device and an aqueous phase containing the analytes is filled into the other side (wide tube). Then the stopcock is opened and the mixture of disperser and extraction solvents mixes with the aqueous phase. By this action, the extraction solvent is dispersed continuously as fine droplets into the aqueous sample and the target analytes are extracted into the fine droplets of the extraction solvent. The fine droplets move up through the aqueous phase due to its low density compared to aqueous phase and collect on the surface of the aqueous phase as an organic layer. Finally an aliquot of the organic phase is removed and injected into the separation system for analysis. Several parameters that can affect extraction efficiency including type and volume of extraction and disperser solvents, sample pH, and ionic strength were investigated and optimized. Under the optimum extraction conditions, the extraction recoveries and enrichment factors ranged from 49 to 74% and 1633 to 2466, respectively. Relative standard deviations were in the ranges of 3-6% (n = 6, C = 30 μg L(-1)) for intra-day and 4-7% (n = 4, C = 30 μg L(-1)) for inter-day precisions. The limits of detection were in the range of 0.20-0.86 μg L(-1). Finally the proposed method was successfully applied to determine the target herbicides in fruit juice and vegetable samples. Copyright © 2016 Elsevier B.V. All rights reserved.

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

Dmowski, W.; Gierlotka, S.; Wang, Z.

Through high-energy x-ray diffraction and atomic pair density function analysis we find that Zr-based metallic alloy, heated to the supercooled liquid state under hydrostatic pressure and then quenched to room temperature, exhibits a distinct glassy structure. The PDF indicates that the Zr-Zr distances in this glass are significantly reduced compared to those quenched without pressure. Annealing at the glass transition temperature at ambient pressure reverses structural changes and the initial glassy state is recovered. This result suggests that pressure causes a liquid-to-liquid phase transition in this metallic alloy supercooled melt. Such a pressure induced transition is known for covalent liquids,more » but has not been observed for metallic liquids. The High Pressure Quenched glasses are stable in ambient conditions after decompression.« less

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.

Phase Equilibria of the Ternary Sn-Pb-Co System at 250°C and Interfacial Reactions of Co with Sn-Pb Alloys

NASA Astrophysics Data System (ADS)

Wang, Chao-hong; Kuo, Chun-yi; Yang, Nian-cih

2015-11-01

The isothermal section of the ternary Sn-Pb-Co system at 250°C was experimentally determined through a series of the equilibrated Sn-Pb-Co alloys of various compositions. The equilibrium phases were identified on the basis of compositional analysis. For the Sn-Co intermetallic compounds (IMCs), CoSn3, CoSn2, CoSn and Co3Sn2, the Pb solubility was very limited. There exist five tie-triangle regions. The Co-Pb system involves one monotectic reaction, so the phase separation of liquid alloys near the Co-Pb side occurred prior to solidification. The immiscibility field was also determined. Additionally, interfacial reactions between Co and Sn-Pb alloys were conducted. The reaction phase for the Sn-48 at.%Pb and Sn-58 at.%Pb at 250°C was CoSn3 and CoSn2, respectively. Both of them were simultaneously formed in the Sn-53 at.%Pb/Co. The formed IMCs were closely associated to the phase equilibria relationship of the liquid-CoSn3-CoSn2 tie-triangle. Furthermore, with increasing temperatures, the phase formed in equilibrium with Sn-37 wt.%Pb was found to transit from CoSn3 to CoSn2 at 275°C. We propose a simple method of examining the phase transition temperature in the interfacial reactions to determine the boundaries of the liquid-CoSn3-CoSn2 tie-triangles at different temperatures.

Chromatographic behavior of small organic compounds in low-temperature high-performance liquid chromatography using liquid carbon dioxide as the mobile phase.

PubMed

Motono, Tomohiro; Nagai, Takashi; Kitagawa, Shinya; Ohtani, Hajime

2015-07-01

Low-temperature high-performance liquid chromatography, in which a loop injector, column, and detection cell were refrigerated at -35ºC, using liquid carbon dioxide as the mobile phase was developed. Small organic compounds (polyaromatic hydrocarbons, alkylbenzenes, and quinones) were separated by low-temperature high-performance liquid chromatography at temperatures from -35 to -5ºC. The combination of liquid carbon dioxide mobile phase with an octadecyl-silica (C18 ) column provided reversed phase mode separation, and a bare silica-gel column resulted in normal phase mode separation. In both the cases, nonlinear behavior at approximately -15ºC was found in the relationship between the temperature and the retention factors of the analytes (van't Hoff plots). In contrast to general trends in high-performance liquid chromatography, the decrease in temperature enhanced the separation efficiency of both the columns. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Immobilization of organic radioactive and non-radioactive liquid waste in a composite matrix

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

Galkin, Anatoliy; Gelis, Artem V.; Castiglioni, Andrew J.

A method for immobilizing liquid radioactive waste is provided, the method having the steps of mixing waste with polymer to form a non-liquid waste; contacting the non-liquid waste with a solidifying agent to create a mixture, heating the mixture to cause the polymer, waste, and filler to irreversibly bind in a solid phase, and compressing the solid phase into a monolith. The invention also provides a method for immobilizing liquid radioactive waste containing tritium, the method having the steps of mixing liquid waste with polymer to convert the liquid waste to a non-liquid waste, contacting the non-liquid waste with amore » solidifying agent to create a mixture, heating the mixture to form homogeneous, chemically stable solid phase, and compressing the chemically stable solid phase into a final waste form, wherein the polymer comprises approximately a 9:1 weight ratio mixture of styrene block co-polymers and cross linked co-polymers of acrylamides.« less

Liquid-liquid phase transition and anomalous diffusion in simulated liquid GeO 2

NASA Astrophysics Data System (ADS)

Hoang, Vo Van; Anh, Nguyen Huynh Tuan; Zung, Hoang

2007-03-01

We perform molecular dynamics (MD) simulation of diffusion in liquid GeO 2 at the temperatures ranged from 3000 to 5000 K and densities ranged from 3.65 to 7.90 g/cm 3. Simulations were done in a model containing 3000 particles with the new interatomic potentials for liquid and amorphous GeO 2, which have weak Coulomb interaction and Morse-type short-range interaction. We found a liquid-liquid phase transition in simulated liquid GeO 2 from a tetrahedral to an octahedral network structure upon compression. Moreover, such phase transition accompanied with an anomalous diffusion of particles in liquid GeO 2 that the diffusion constant of both Ge and O particles strongly increases with increasing density (e.g. with increasing pressure) and it shows a maximum at the density around 4.95 g/cm 3. The possible relation between anomalous diffusion of particles and structural phase transition in the system has been discussed.

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.

Pressure-Induced Phase Transitions of n-Tridecane

NASA Astrophysics Data System (ADS)

Yamashita, Motoi

Pressure-induced phase transition behavior of n-tridecane from the ordered phase through the rotator phase into the liquid phase has been investigated by using Fourier transform infrared spectroscopy at 25 °C. The transition between the ordered and rotator phases has been observed in the pressure range of 270-220 MPa and the transition between the rotator and liquid phases has been observed in the pressure range of 171-112 MPa, within the experimental error of ±50 MPa. The populations of the -gtg- + -gtg'-, -gg- and gt- defects determined from the methylene wagging mode are smaller in the rotator phase than in the liquid phase and are smaller under higher pressure in both of the rotator and liquid phases. A relationship has been found between the conformation and the intensity of the 890 cm-1 band, which has been assigned as the methyl rocking mode and has been considered as insensitive to conformation.

Determination of partition coefficient and analysis of nitrophenols by three-phase liquid-phase microextraction coupled with capillary electrophoresis.

PubMed

Sanagi, Mohd Marsin; Miskam, Mazidatulakmam; Wan Ibrahim, Wan Aini; Hermawan, Dadan; Aboul-Enein, Hassan Y

2010-07-01

A three-phase hollow fiber liquid-phase microextraction method coupled with CE was developed and used for the determination of partition coefficients and analysis of selected nitrophenols in water samples. The selected nitrophenols were extracted from 14 mL of aqueous solution (donor solution) with the pH adjusted to pH 3 into an organic phase (1-octanol) immobilized in the pores of the hollow fiber and finally backextracted into 40.0 microL of the acceptor phase (NaOH) at pH 12.0 located inside the lumen of the hollow fiber. The extractions were carried out under the following optimum conditions: donor solution, 0.05 M H(3)PO(4), pH 3.0; organic solvent, 1-octanol; acceptor solution, 40 microL of 0.1 M NaOH, pH 12.0; agitation rate, 1050 rpm; extraction time, 15 min. Under optimized conditions, the calibration curves for the analytes were linear in the range of 0.05-0.30 mg/L with r(2)>0.9900 and LODs were in the range of 0.01-0.04 mg/L with RSDs of 1.25-2.32%. Excellent enrichment factors of up to 398-folds were obtained. It was found that the partition coefficient (K(a/d)) values were high for 2-nitrophenol, 3-nitrophenol, 4-nitrophenol, 2,4-dinitrophenol and 2,6-dinitrophenol and that the individual partition coefficients (K(org/d) and K(a/org)) promoted efficient simultaneous extraction from the donor through the organic phase and further into the acceptor phase. The developed method was successfully applied for the analysis of water samples.

Laser-induced separation of hydrogen isotopes in the liquid phase

DOEpatents

Freund, Samuel M.; Maier, II, William B.; Beattie, Willard H.; Holland, Redus F.

1980-01-01

Hydrogen isotope separation is achieved by either (a) dissolving a hydrogen-bearing feedstock compound in a liquid solvent, or (b) liquefying a hydrogen-bearing feedstock compound, the liquid phase thus resulting being kept at a temperature at which spectral features of the feedstock relating to a particular hydrogen isotope are resolved, i.e., a clear-cut isotope shift is delineated, irradiating the liquid phase with monochromatic radiation of a wavelength which at least preferentially excites those molecules of the feedstock containing a first hydrogen isotope, inducing photochemical reaction in the excited molecules, and separating the reaction product containing the first isotope from the liquid phase.

Binary Solid-Liquid Phase Diagram of Phenol and t-Butanol: An Undergraduate Physical Chemistry Experiment

ERIC Educational Resources Information Center

Xu, Xinhua; Wang, Xiaogang; Wu, Meifen

2014-01-01

The determination of the solid-liquid phase diagram of a binary system is always used as an experiment in the undergraduate physical chemistry laboratory courses. However, most phase diagrams investigated in the lab are simple eutectic ones, despite the fact that complex binary solid-liquid phase diagrams are more common. In this article, the…

Modeling of Liquid Steel/Slag/Argon Gas Multiphase Flow During Tundish Open Eye Formation in a Two-Strand Tundish

NASA Astrophysics Data System (ADS)

Chatterjee, Saikat; Li, Donghui; Chattopadhyay, Kinnor

2018-04-01

Multiphase flows are frequently encountered in metallurgical operations. One of the most effective ways to understand these processes is by flow modeling. The process of tundish open eye (TOE) formation involves three-phase interaction between liquid steel, slag, and argon gas. The two-phase interaction involving argon gas bubbles and liquid steel can be modeled relatively easily using the discrete phase modeling technique. However, the effect of an upper slag layer cannot be captured using this approach. The presence of an upper buoyant phase can have a major effect on the behavior of TOEs. Hence, a multiphase model, including three phases, viz. liquid steel, slag, and argon gas, in a two-strand slab caster tundish, was developed to study the formation and evolution of TOEs. The volume of fluid model was used to track the interphase between liquid steel and slag phases, while the discrete phase model was used to trace the movement of the argon gas bubbles in liquid steel. The variation in the TOE areas with different amounts of aspirated argon gas was examined in the presence of an overlying slag phase. The mathematical model predictions were compared against steel plant measurements.

Study on stainless steel electrode based on dynamic aluminum liquid corrosion mechanism.

PubMed

Hou, Hua; Yang, Ruifeng

2009-01-01

Scanning electrion microscope (SEM) was performed for investigations on the corrosion mechanism of stainless steel electrode in dynamic melting aluminum liquid. Microstructures and composition analysis was made by electron probe analysis (EPA) combined with metallic phase analysis. It can be concluded that the corrosion process is mainly composed of physical corrosion (flowing and scouring corrosion) and chemical corrosion (forming FeAl and Fe2Al5) and the two mechanisms usually exist simultaneously. The corrosion interface thickness is about 10 μm, which is different to usual interface width of hundreds μm in the static melting Al with iron matrix.

Ultra-high performance liquid chromatography with fluorescence detection following salting-out assisted liquid-liquid extraction for the analysis of benzimidazole residues in farm fish samples.

PubMed

Tejada-Casado, Carmen; Lara, Francisco J; García-Campaña, Ana M; Del Olmo-Iruela, Monsalud

2018-03-30

Ultra-high performance liquid chromatography (UHPLC) coupled with fluorescence detection (FL) has been proposed for the first time to determine thirteen benzimidazoles (BZs) in farmed fish samples. In order to optimize the chromatographic separation, parameters such as mobile phase composition and flow rate were carefully studied, establishing a gradient mode with a mobile phase consisted of water (solvent A) and acetonitrile (solvent B) at a flow rate of 0.4 mL/min. The separation was performed on a Zorbax Eclipse Plus RRHD C 18 column (50 × 2.1 mm, 1.8 μm), involving a total analysis time lower than 12 min. Salting-out assisted liquid-liquid extraction (SALLE) was applied as sample treatment to different types of farmed fish (trout, sea bream and sea bass). To obtain satisfactory extraction efficiencies for the studied analytes, several parameters affecting the SALLE procedure were optimized including the amount of sample, type and volume of the extraction solvent, and the nature and amount of the salt used. Characterization of the method in terms of performance characteristics was carried out, obtaining satisfactory results for the linearity (R 2  ≥ 0.997), repeatability (RSD ≤ 6.1%), reproducibility (RSD ≤ 10.8%) and recoveries (R ≥ 79%; RSD ≤ 7.8%). Detection limits between 0.04-29.9 μg kg -1 were obtained, demonstrating the applicability of this fast, simple and environmentally friendly method. Copyright © 2018 Elsevier B.V. All rights reserved.

Multi-residue determination of the sorption of illicit drugs and pharmaceuticals to wastewater suspended particulate matter using pressurised liquid extraction, solid phase extraction and liquid chromatography coupled with tandem mass spectrometry.

PubMed

Baker, David R; Kasprzyk-Hordern, Barbara

2011-11-04

Presented is the first comprehensive study of drugs of abuse on suspended particulate matter (SPM) in wastewater. Analysis of SPM is crucial to prevent the under-reporting of the levels of analyte that may be present in wastewater. Analytical methods to date analyse the aqueous part of wastewater samples only, removing SPM through the use of filtration or centrifugation. The development of an analytical method to determine 60 compounds on SPM using a combination of pressurised liquid extraction, solid phase extraction and liquid chromatography coupled with tandem mass spectrometry (PLE-SPE-LC-MS/MS) is reported. The range of compounds monitored included stimulants, opioid and morphine derivatives, benzodiazepines, antidepressants, dissociative anaesthetics, drug precursors, and their metabolites. The method was successfully validated (parameters studied: linearity and range, recovery, accuracy, reproducibility, repeatability, matrix effects, and limits of detection and quantification). The developed methodology was applied to SPM samples collected at three wastewater treatment plants in the UK. The average proportion of analyte on SPM as opposed to in the aqueous phase was <5% for several compounds including cocaine, benzoylecgonine, MDMA, and ketamine; whereas the proportion was >10% with regard to methadone, EDDP, EMDP, BZP, fentanyl, nortramadol, norpropoxyphene, sildenafil and all antidepressants (dosulepin, amitriptyline, nortriptyline, fluoxetine and norfluoxetine). Consequently, the lack of SPM analysis in wastewater sampling protocol could lead to the under-reporting of the measured concentration of some compounds. Copyright © 2011 Elsevier B.V. All rights reserved.

Gaining insight in the behaviour of imidazolium-based ionic liquids as additives in reversed-phase liquid chromatography for the analysis of basic compounds.

PubMed

Ubeda-Torres, M T; Ortiz-Bolsico, C; García-Alvarez-Coque, M C; Ruiz-Angel, M J

2015-02-06

In reversed-phase liquid chromatography in the absence of additives, cationic basic compounds give rise to broad and asymmetrical peaks as a result of ionic interactions with residual free silanols on silica-based stationary phases. Ionic liquids (ILs), added to the mobile phase, have been suggested as alternatives to amines to block the activity of silanols. However, the dual character of ILs should be considered: both cation and anion may be adsorbed on the stationary phase, thereby creating a double asymmetrical layer positively or negatively charged, depending on the relative adsorption of both ions. In this work, a study of the performance of six imidazolium-based ILs (the chlorides and tetrafluoroborates of 1-ethyl-, 1-butyl- and 1-hexyl-3-methylimidazolium) as modifiers of the chromatographic behaviour of a group of 10 β-blockers is performed, and compared with triethylamine and dimethyloctylamine. In order to gain more insight in the behaviour of ILs in RPLC, the changes in the nature of the chromatographic system, at increasing concentration of the additives, were followed based on retention and peak shape modelling. The multiple interactions that amines and ILs experience inside the chromatographic system suggest that the suppressing potency should be measured based on the shape of chromatographic peaks and not on the changes in retention. The ILs 1-hexyl-3-methyl-imidazolium chloride and tetrafluoroborate offered the most interesting features for the separation of the basic drugs. Copyright © 2014 Elsevier B.V. All rights reserved.

Dynamic Modeling Strategy for Flow Regime Transition in Gas-Liquid Two-Phase Flows

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

Xia Wang; Xiaodong Sun; Benjamin Doup

In modeling gas-liquid two-phase flows, the concept of flow regimes has been widely used to characterize the global interfacial structure of the flows. Nearly all constitutive relations that provide closures to the interfacial transfers in two-phase flow models, such as the two-fluid model, are flow regime dependent. Current nuclear reactor safety analysis codes, such as RELAP5, classify flow regimes using flow regime maps or transition criteria that were developed for steady-state, fully-developed flows. As twophase flows are dynamic in nature, it is important to model the flow regime transitions dynamically to more accurately predict the two-phase flows. The present workmore » aims to develop a dynamic modeling strategy to determine flow regimes in gas-liquid two-phase flows through introduction of interfacial area transport equations (IATEs) within the framework of a two-fluid model. The IATE is a transport equation that models the interfacial area concentration by considering the creation of the interfacial area, fluid particle (bubble or liquid droplet) disintegration, boiling and evaporation, and the destruction of the interfacial area, fluid particle coalescence and condensation. For flow regimes beyond bubbly flows, a two-group IATE has been proposed, in which bubbles are divided into two groups based on their size and shapes, namely group-1 and group-2 bubbles. A preliminary approach to dynamically identify the flow regimes is discussed, in which discriminator s are based on the predicted information, such as the void fraction and interfacial area concentration. The flow regime predicted with this method shows good agreement with the experimental observations.« less

Current and Future Critical Issues in Rocket Propulsion Systems

NASA Technical Reports Server (NTRS)

Navaz, Homayun K.; Dix, Jeff C.

1998-01-01

The objective of this research was to tackle several problems that are currently of great importance to NASA. In a liquid rocket engine several complex processes take place that are not thoroughly understood. Droplet evaporation, turbulence, finite rate chemistry, instability, and injection/atomization phenomena are some of the critical issues being encountered in a liquid rocket engine environment. Pulse Detonation Engines (PDE) performance, combustion chamber instability analysis, 60K motor flowfield pattern from hydrocarbon fuel combustion, and 3D flowfield analysis for the Combined Cycle engine were of special interest to NASA. During the summer of 1997, we made an attempt to generate computational results for all of the above problems and shed some light on understanding some of the complex physical phenomena. For this purpose, the Liquid Thrust Chamber Performance (LTCP) code, mainly designed for liquid rocket engine applications, was utilized. The following test cases were considered: (1) Characterization of a detonation wave in a Pulse Detonation Tube; (2) 60K Motor wall temperature studies; (3) Propagation of a pressure pulse in a combustion chamber (under single and two-phase flow conditions); (4) Transonic region flowfield analysis affected by viscous effects; (5) Exploring the viscous differences between a smooth and a corrugated wall; and (6) 3D thrust chamber flowfield analysis of the Combined Cycle engine. It was shown that the LTCP-2D and LTCP-3D codes are capable of solving complex and stiff conservation equations for gaseous and droplet phases in a very robust and efficient manner. These codes can be run on a workstation and personal computers (PC's).

Phase behavior of metastable liquid silicon at negative pressure: Ab initio molecular dynamics

NASA Astrophysics Data System (ADS)

Zhao, G.; Yu, Y. J.; Yan, J. L.; Ding, M. C.; Zhao, X. G.; Wang, H. Y.

2016-04-01

Extensive first-principle molecular dynamics simulations are performed to study the phase behavior of metastable liquid Si at negative pressure. Our results show that the high-density liquid (HDL) and HDL-vapor spinodals indeed form a continuous reentrant curve and the liquid-liquid critical point seems to just coincide with its minimum. The line of density maxima also has a strong tendency to pass through this minimum. The phase behaviour of metastable liquid Si therefore tends to be a critical-point-free scenario rather than a second-critical-point one based on SW potential.

Analysis of fusaric acid in maize using molecularly imprinted solid phase extraction (MISPE) clean-up and ion-pair LC with diode array UV detection

USDA-ARS?s Scientific Manuscript database

Fusaric acid is a phytotoxin and mycotoxin occasionally found in maize contaminated with Fusarium fungi. A selective sample clean-up procedure was developed to detect fusaric acid in maize using molecularly imprinted solid phase extraction (MISPE) clean-up coupled with ion-pair liquid chromatography...

Rapid Analysis of Chemical Warfare Agents and Their Hydrolysis Products by Desorption Electrospray Ionization Mass Spectrometry (DESI-MS)

DTIC Science & Technology

2009-10-01

of chemical warfare agents in natural water samples by solid-phase microextraction. Anal. Chem., 69, 1866-72. [36] Sng , M.T. and Ng ,W.F. (1999). In...liquid phase microextraction of alkylphosphonic acids from water. J. Chromatogr. A., 1141, 151-157. [43] Lee, H.S.N., Sng , M.T., Basheer, C., and Lee

A High Resolution Hydrometer Phase Classifier Based on Analysis of Cloud Radar Doppler Spectra.

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

Luke,E.; Kollias, P.

2007-08-06

The lifecycle and radiative properties of clouds are highly sensitive to the phase of their hydrometeors (i.e., liquid or ice). Knowledge of cloud phase is essential for specifying the optical properties of clouds, or else, large errors can be introduced in the calculation of the cloud radiative fluxes. Current parameterizations of cloud water partition in liquid and ice based on temperature are characterized by large uncertainty (Curry et al., 1996; Hobbs and Rangno, 1998; Intriery et al., 2002). This is particularly important in high geographical latitudes and temperature ranges where both liquid droplets and ice crystal phases can exist (mixed-phasemore » cloud). The mixture of phases has a large effect on cloud radiative properties, and the parameterization of mixed-phase clouds has a large impact on climate simulations (e.g., Gregory and Morris, 1996). Furthermore, the presence of both ice and liquid affects the macroscopic properties of clouds, including their propensity to precipitate. Despite their importance, mixed-phase clouds are severely understudied compared to the arguably simpler single-phase clouds. In-situ measurements in mixed-phase clouds are hindered due to aircraft icing, difficulties distinguishing hydrometeor phase, and discrepancies in methods for deriving physical quantities (Wendisch et al. 1996, Lawson et al. 2001). Satellite-based retrievals of cloud phase in high latitudes are often hindered by the highly reflecting ice-covered ground and persistent temperature inversions. From the ground, the retrieval of mixed-phase cloud properties has been the subject of extensive research over the past 20 years using polarization lidars (e.g., Sassen et al. 1990), dual radar wavelengths (e.g., Gosset and Sauvageot 1992; Sekelsky and McIntosh, 1996), and recently radar Doppler spectra (Shupe et al. 2004). Millimeter-wavelength radars have substantially improved our ability to observe non-precipitating clouds (Kollias et al., 2007) due to their excellent sensitivity that enables the detection of thin cloud layers and their ability to penetrate several non-precipitating cloud layers. However, in mixed-phase clouds conditions, the observed Doppler moments are dominated by the highly reflecting ice crystals and thus can not be used to identify the cloud phase. This limits our ability to identify the spatial distribution of cloud phase and our ability to identify the conditions under which mixed-phase clouds form.« less

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.

Analysis of iodinated haloacetic acids in drinking water by reversed-phase liquid chromatography/electrospray ionization/tandem mass spectrometry with large volume direct aqueous injection.

PubMed

Li, Yongtao; Whitaker, Joshua S; McCarty, Christina L

2012-07-06

A large volume direct aqueous injection method was developed for the analysis of iodinated haloacetic acids in drinking water by using reversed-phase liquid chromatography/electrospray ionization/tandem mass spectrometry in the negative ion mode. Both the external and internal standard calibration methods were studied for the analysis of monoiodoacetic acid, chloroiodoacetic acid, bromoiodoacetic acid, and diiodoacetic acid in drinking water. The use of a divert valve technique for the mobile phase solvent delay, along with isotopically labeled analogs used as internal standards, effectively reduced and compensated for the ionization suppression typically caused by coexisting common inorganic anions. Under the optimized method conditions, the mean absolute and relative recoveries resulting from the replicate fortified deionized water and chlorinated drinking water analyses were 83-107% with a relative standard deviation of 0.7-11.7% and 84-111% with a relative standard deviation of 0.8-12.1%, respectively. The method detection limits resulting from the external and internal standard calibrations, based on seven fortified deionized water replicates, were 0.7-2.3 ng/L and 0.5-1.9 ng/L, respectively. Copyright © 2012 Elsevier B.V. All rights reserved.

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.

Possible realization of interacting symmetry-protected topological phases in topological crystalline insulators

NASA Astrophysics Data System (ADS)

Isobe, Hiroki; Fu, Liang

2015-03-01

The effects of electron-electron interaction in edge states of mirror-symmetry protected topological crystalline insulators (TCI's) are discussed. The analysis is performed by using bosonized Hamiltonian following the Tomonaga-Luttinger liquid theory. When two pairs of helical edge states exist, electron-electron interaction could gap out one edge mode, which is a possible realization of interacting symmetry-protected topological (SPT) phases. This type of SPT phase is closely related to a Luther-Emery liquid in spinful 1D system. We also propose a method of detecting the SPT phases by STM. The other focus of the study is the classification of SPT phases in mirror-symmetry protected TCI's. By adopting the Chern-Simons theory, we find that electron-electron interaction reduces the classification from Z to Z4. It means that the edge states can be gapped out when four pairs of edge states exist. In other cases, the edge modes cannot be fully gapped. Each of these states corresponds to a different SPT phase depending on the relevant interaction process.

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

PubMed Central

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

2012-01-01

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

Process for Encapsulating Protein Crystals

NASA Technical Reports Server (NTRS)

Morrison, Dennis R.; Mosier, Benjamin

2003-01-01

A process for growing protein crystals encapsulated within membranes has been invented. This process begins with the encapsulation of a nearly saturated aqueous protein solution inside semipermeable membranes to form microcapsules. The encapsulation is effected by use of special formulations of a dissolved protein and a surfactant in an aqueous first liquid phase, which is placed into contact with a second, immiscible liquid phase that contains one or more polymers that are insoluble in the first phase. The second phase becomes formed into the semipermeable membranes that surround microglobules of the first phase, thereby forming the microcapsules. Once formed, the microcapsules are then dehydrated osmotically by exposure to a concentrated salt or polymer solution. The dehydration forms supersaturated solutions inside the microcapsules, thereby enabling nucleation and growth of protein crystals inside the microcapsules. By suitable formulation of the polymer or salt solution and of other physical and chemical parameters, one can control the rate of transport of water out of the microcapsules through the membranes and thereby create physicochemical conditions that favor the growth, within each microcapsule, of one or a few large crystals suitable for analysis by x-ray diffraction. The membrane polymer can be formulated to consist of low-molecular-weight molecules that do not interfere with the x-ray diffraction analysis of the encapsulated crystals. During dehydration, an electrostatic field can be applied to exert additional control over the rate of dehydration. This protein-crystal-encapsulation process is expected to constitute the basis of protein-growth experiments to be performed on the space shuttle and the International Space Station. As envisioned, the experiments would involve the exposure of immiscible liquids to each other in sequences of steps under microgravitational conditions. The experiments are expected to contribute to knowledge of the precise conditions under which protein crystals form. By enhancing the ability to grow crystals suitable for x-ray diffraction analysis, this knowledge can be expected to benefit not only the space program but also medicine and the pharmaceutical industry.

Quasi-targeted analysis of hydroxylation-related metabolites of polycyclic aromatic hydrocarbons in human urine by liquid chromatography-mass spectrometry.

PubMed

Tang, Caiming; Tan, Jianhua; Fan, Ruifang; Zhao, Bo; Tang, Caixing; Ou, Weihui; Jin, Jiabin; Peng, Xianzhi

2016-08-26

Metabolite identification is crucial for revealing metabolic pathways and comprehensive potential toxicities of polycyclic aromatic hydrocarbons (PAHs) in human body. In this work, a quasi-targeted analysis strategy was proposed for metabolite identification of monohydroxylated polycyclic aromatic hydrocarbons (OH-PAHs) in human urine using liquid chromatography triple quadruple mass spectrometry (LC-QqQ-MS/MS) combined with liquid chromatography high resolution mass spectrometry (LC-HRMS). Potential metabolites of OH-PAHs were preliminarily screened out by LC-QqQ-MS/MS in association with filtering in a self-constructed information list of possible metabolites, followed by further identification and confirmation with LC-HRMS. The developed method can provide more reliable and systematic results compared with traditional untargeted analysis using LC-HRMS. In addition, data processing for LC-HRMS analysis were greatly simplified. This quasi-targeted analysis method was successfully applied to identifying phase I and phase II metabolites of OH-PAHs in human urine. Five metabolites of hydroxynaphthalene, seven of hydroxyfluorene, four of hydroxyphenanthrene, and three of hydroxypyrene were tentatively identified. Metabolic pathways of PAHs in human body were putatively revealed based on the identified metabolites. The experimental results will be valuable for investigating the metabolic processes of PAHs in human body, and the quasi-targeted analysis strategy can be expanded to the metabolite identification and profiling of other compounds in vivo. Copyright © 2016 Elsevier B.V. All rights reserved.

Hollow fibre-based liquid phase microextraction combined with high-performance liquid chromatography for the analysis of flavonoids in Echinophora platyloba DC. and Mentha piperita.

PubMed

Hadjmohammadi, Mohammadreza; Karimiyan, Hanieh; Sharifi, Vahid

2013-11-15

A simple, inexpensive and efficient three phase hollow fibre liquid phase microextraction (HF-LPME) technique combined with HPLC was used for the simultaneous determination of flavonoids in Echinophora platyloba DC. and Mentha piperita. Different factors affecting the HF-LPME procedure were investigated and optimised. The optimised extraction conditions were as follows: 1-octanol as an organic solvent, pHdonor=2, pHacceptor=9.75, stirring rate of 1000rpm, extraction time of 80min, without addition of salt. Under these conditions, the enrichment factors ranged between 146 and 311. The values of intra and inter-day relative standard deviations (RSD) were in the range of 3.18-6.00% and 7.25-11.00%, respectively. The limits of detection (LODs) ranged between 0.5 and 7.0ngmL(-1). Among the investigated flavonoids quercetin was found in E. platyloba DC. and luteolin was found in M. piperita. Concentration of quercetin and luteolin was 0.015 and 0.025mgg(-1) respectively. Copyright © 2013 Elsevier Ltd. All rights reserved.