Reduction of Solvent Effect in Reverse Phase Gradient Elution LC-ICP-MS

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

Sullivan, Patrick Allen

2005-12-17

Quantification in liquid chromatography (LC) is becoming very important as more researchers are using LC, not as an analytical tool itself, but as a sample introduction system for other analytical instruments. The ability of LC instrumentation to quickly separate a wide variety of compounds makes it ideal for analysis of complex mixtures. For elemental speciation, LC is joined with inductively coupled plasma mass spectrometry (ICP-MS) to separate and detect metal-containing, organic compounds in complex mixtures, such as biological samples. Often, the solvent gradients required to perform complex separations will cause matrix effects within the plasma. This limits the sensitivity ofmore » the ICP-MS and the quantification methods available for use in such analyses. Traditionally, isotope dilution has been the method of choice for LC-ICP-MS quantification. The use of naturally abundant isotopes of a single element in quantification corrects for most of the effects that LC solvent gradients produce within the plasma. However, not all elements of interest in speciation studies have multiple naturally occurring isotopes; and polyatomic interferences for a given isotope can develop within the plasma, depending on the solvent matrix. This is the case for reverse phase LC separations, where increasing amounts of organic solvent are required. For such separations, an alternative to isotope dilution for quantification would be is needed. To this end, a new method was developed using the Apex-Q desolvation system (ESI, Omaha, NE) to couple LC instrumentation with an ICP-MS device. The desolvation power of the system allowed greater concentrations of methanol to be introduced to the plasma prior to destabilization than with direct methanol injection into the plasma. Studies were performed, using simulated and actual linear methanol gradients, to find analyte-internal standard (AIS) pairs whose ratio remains consistent (deviations {+-} 10%) over methanol concentration ranges of 5%-35% (simulated) and 8%-32% (actual). Quadrupole (low resolution) and sector field (high resolution) ICP-MS instrumentation were utilized in these studies. Once an AIS pair is determined, quantification studies can be performed. First, an analysis is performed by adding both elements of the AIS pair post-column while performing the gradient elution without sample injection. A comparison of the ratio of the measured intensities to the atomic ratio of the two standards is used to determine a correction factor that can be used to account for the matrix effects caused by the mobile phase. Then, organic and/or biological molecules containing one of the two elements in the AIS pair are injected into the LC column. A gradient method is used to vary the methanol-water mixture in the mobile phase and to separate out the compounds in a given sample. A standard solution of the second ion in the AIS pair is added continuously post-column. By comparing the ratio of the measured intensities to the atomic ratio of the eluting compound and internal standard, the concentration of the injected compound can be determined.« less

[Simultaneous determination of five cold medicine ingredients in paracetamol triprolidine hydrochloride and pseudoephedrine hydrochloride tablets by pH/organic solvent double-gradient high performance liquid chromatography].

PubMed

Xuan, Xueyi; Huang, Lina; Pan, Xiaoling; Li, Ning

2013-02-01

A pH/organic solvent double-gradient mode in reversed-phase high performance liquid chromatography (HPLC) has been established as a new approach to the simultaneous determination of acetaminophen, caffeine, salicylamide, pseudoephedrine hydrochloride and triprolidine hydrochloride in paracetamol triprolidine hydrochloride and pseudoephedrine hydrochloride tablets. Through the optimization of the organic solvent gradient mode and pH/organic solvent double-gradient mode, the optimum double-gradient HPLC system of the five cold medicine ingredients has been built. The determination was carried out on a Diamonsiol C18 column (250 mm x 4.6 mm, 5 microm). The mobile phase consisted of methanol, 0.05 mol/L ammonium acetate solution and 0.08 mol/L acetic acid solution. The column temperature was set at 30 degrees C. The flow rate was 1.0 mL/min. The sample was measured at multiple wavelengths: 0-6 min, 280 nm; 6-7 min, 257 nm; 7-14 min, 280 nm; 14 min, 233 nm. The separation of the five cold medicine ingredients in the tablets was achieved in 25.5 min. The linear ranges of acetaminophen, pseudoephedrine hydrochloride, caffeine, salicylamide and triprolidine hydrochloride were 0.055 -0.998 g/L, 0.053-0.946 g/L, 0.007-0.129 g/L, 0.035-0.622 g/L and 0.002-0.039 g/L, respectively, with their correlation coefficients greater than 0.999 0. The detection limits (S/N = 3) were 0.09, 6, 0.02, 0.128 and 0.02 mg/L, respectively. Their mean recoveries were 97.9%-102.8%. The advantage of the method is the simultaneous determination of acidic, neutral and basic compounds. It also can improve the column efficiency of the analyte, compress the half-peak width and reduce the trailing. The optimized and validated method can be used for the simultaneous determination of the five cold medicine ingredients in the tablets.

Size exclusion chromatography-gradients, an alternative approach to polymer gradient chromatography: 2. Separation of poly(meth)acrylates using a size exclusion chromatography-solvent/non-solvent gradient.

PubMed

Schollenberger, Martin; Radke, Wolfgang

2011-10-28

A gradient ranging from methanol to tetrahydrofuran (THF) was applied to a series of poly(methyl methacrylate) (PMMA) standards, using the recently developed concept of SEC-gradients. Contrasting to conventional gradients the samples eluted before the solvent, i.e. within the elution range typical for separations by SEC, however, the high molar mass PMMAs were retarded as compared to experiments on the same column using pure THF as the eluent. The molar mass dependence on retention volume showed a complex behaviour with a nearly molar mass independent elution for high molar masses. This molar mass dependence was explained in terms of solubility and size exclusion effects. The solubility based SEC-gradient was proven to be useful to separate PMMA and poly(n-butyl crylate) (PnBuA) from a poly(t-butyl crylate) (PtBuA) sample. These samples could be separated neither by SEC in THF, due to their very similar hydrodynamic volumes, nor by an SEC-gradient at adsorbing conditions, due to a too low selectivity. The example shows that SEC-gradients can be applied not only in adsorption/desorption mode, but also in precipitation/dissolution mode without risking blocking capillaries or breakthrough peaks. Thus, the new approach is a valuable alternative to conventional gradient chromatography. Copyright © 2011 Elsevier B.V. All rights reserved.

Controlling microtube permeability via grafted polymers and solvent quality.

PubMed

Suo, Tongchuan; Whitmore, Mark D

2014-03-21

We examine pressure-driven flow through a microtube with grafted polymers using a "doubly self-consistent field" steady-state theory. Our focus is on the structure of the polymer layer, the tube permeability, and the effects of solvent quality, for different regimes of open and closed tubes. We find that, within experimentally attainable pressure gradients, the flow has very little effect on the grafted layer. However, the polymers, and in particular variations in the solvent quality and cylinder radii, can have large effects on the flow. We find that the permeability can either increase or decrease with either the radius or solvent quality, and we identify the regimes for different behaviors in terms of general parameters that can be used to generalize to other systems. This allows us to identify regimes where the systems are most sensitive to these "tuning" parameters, and we find that they correspond to the boundaries between open and closed tubes identified earlier.

Solvent Flux Method (SFM): A Case Study of Water Access to Candida antarctica Lipase B.

PubMed

Benson, Sven P; Pleiss, Jürgen

2014-11-11

The solvent flux method (SFM) was developed to comprehensively characterize the influx of solvent molecules from the solvent environment into the active site of a protein in the framework of molecular dynamics simulations. This was achieved by introducing a solvent concentration gradient as well as partially reorienting and rescaling the velocity vector of all solvent molecules contained within a spherical volume enclosing the protein, thus inducing an accelerated solvent influx toward the active site. In addition to the detection of solvent access pathway within the protein structure, it is hereby possible to identify potential amino acid positions relevant to solvent-related enzyme engineering with high statistical significance. The method is particularly aimed at improving the reverse hydrolysis reaction rates in nonaqueous media. Candida antarctica lipase B (CALB) binds to a triglyceride-water interface with its substrate entrance channel oriented toward the hydrophobic substrate interface. The lipase-triglyceride-water system served as a model system for SFM to evaluate the influx of water molecules to the active site. As a proof of principle for SFM, a previously known water access pathway in CALB was identified as the primary water channel. In addition, a secondary water channel and two pathways for water access which contribute to water leakage between the protein and the triglyceride-water interface were identified.

Analytical RISM-MP2 free energy gradient method: Application to the Schlenk equilibrium of Grignard reagent

NASA Astrophysics Data System (ADS)

Mori, Toshifumi; Kato, Shigeki

2007-03-01

We present a method to evaluate the analytical gradient of reference interaction site model Møller-Plesset second order free energy with respect to solute nuclear coordinates. It is applied to calculate the geometries and energies in the equilibria of the Grignard reagent (CH 3MgCl) in dimethylether solvent. The Mg-Mg and Mg-Cl distances as well as the binding energies of solvents are largely affected by the dynamical electron correlation. The solvent effect on the Schlenk equilibrium is examined.

Monitoring gradient profile on-line in micro- and nano-high performance liquid chromatography using conductivity detection.

PubMed

Zhang, Min; Chen, Apeng; Lu, Joann J; Cao, Chengxi; Liu, Shaorong

2016-08-19

In micro- or nano-flow high performance liquid chromatography (HPLC), flow-splitters and gradient elutions are commonly used for reverse phase HPLC separations. When a flow splitter was used at a high split-ratio (e.g., 1000:1 or higher), the actual gradient may deviate away from the programmed gradient. Sometimes, mobile phase concentrations can deviate by as much as 5%. In this work, we noticed that the conductivity (σ) of a gradient decreased with the increasing organic-solvent fraction (φ). Based on the relationship between σ and φ, a method was developed for monitoring gradient profile on-line to record any deviations in these HPLC systems. The conductivity could be measured by a traditional conductivity detector or a capacitively coupled contactless conductivity detector (C(4)D). The method was applied for assessing the performance of an electroosmotic pump (EOP) based nano-HPLC. We also observed that σ value of the gradient changed with system pressure; a=0.0175ΔP (R(2)=0.964), where a is the percentage of the conductivity increase and ΔP is the system pressure in bar. This effect was also investigated. Copyright © 2016. Published by Elsevier B.V.

“Measure Your Gradient”: A New Way to Measure Gradients in High Performance Liquid Chromatography by Mass Spectrometric or Absorbance Detection

PubMed Central

Magee, Megan H.; Manulik, Joseph C.; Barnes, Brian B.; Abate-Pella, Daniel; Hewitt, Joshua T.; Boswell, Paul G.

2014-01-01

The gradient produced by an HPLC is never the same as the one it is programmed to produce, but non-idealities in the gradient can be taken into account if they are measured. Such measurements are routine, yet only one general approach has been described to make them: both HPLC solvents are replaced with water, solvent B is spiked with 0.1% acetone, and the gradient is measured by UV absorbance. Despite the widespread use of this procedure, we found a number of problems and complications with it, mostly stemming from the fact that it measures the gradient under abnormal conditions (e.g. both solvents are water). It is also generally not amenable to MS detection, leaving those with only an MS detector no way to accurately measure their gradients. We describe a new approach called “Measure Your Gradient” that potentially solves these problems. One runs a test mixture containing 20 standards on a standard stationary phase and enters their gradient retention times into open-source software available at www.measureyourgradient.org. The software uses the retention times to back-calculate the gradient that was truly produced by the HPLC. Here we present a preliminary investigation of the new approach. We found that gradients measured this way are comparable to those measured by a more accurate, albeit impractical, version of the conventional approach. The new procedure worked with different gradients, flow rates, column lengths, inner diameters, on two different HPLCs, and with six different batches of the standard stationary phase. PMID:25441073

ANALYSIS OF PROTEIN DIGESTS BY nano- SCX/RP/MSMS WITH pH SALT GRADIENT SCX ELUTION

EPA Science Inventory

The objective of this study was to optimize chromatographic parameters for complex peptide mixture analyses using two dimensional nano-LC/MSMS system. It used a strong cation exchange (SCX) and reversed phase chromatography (RP). The SCX solvent system was designed to promote pep...

Highly sensitive detection of naphthalene in solvent vapor using a functionalized PBG refractive index sensor.

PubMed

Girschikofsky, Maiko; Rosenberger, Manuel; Belle, Stefan; Brutschy, Malte; Waldvogel, Siegfried R; Hellmann, Ralf

2012-01-01

We report an optical refractive index sensor system based on a planar Bragg grating which is functionalized by substituted γ-cyclodextrin to determine low concentrations of naphthalene in solvent vapor. The sensor system exhibits a quasi-instantaneous shift of the Bragg wavelength and is therefore capable for online detection. The overall shift of the Bragg wavelength reveals a linear relationship to the analyte concentration with a gradient of 12.5 ± 1.5 pm/ppm. Due to the spectral resolution and repeatability of the interrogation system, this corresponds to acquisition steps of 80 ppb. Taking into account the experimentally detected signal noise a minimum detection limit of 0.48 ± 0.05 ppm is deduced.

Solvent effects in time-dependent self-consistent field methods. II. Variational formulations and analytical gradients

DOE PAGES

Bjorgaard, J. A.; Velizhanin, K. A.; Tretiak, S.

2015-08-06

This study describes variational energy expressions and analytical excited state energy gradients for time-dependent self-consistent field methods with polarizable solvent effects. Linear response, vertical excitation, and state-specific solventmodels are examined. Enforcing a variational ground stateenergy expression in the state-specific model is found to reduce it to the vertical excitation model. Variational excited state energy expressions are then provided for the linear response and vertical excitation models and analytical gradients are formulated. Using semiempiricalmodel chemistry, the variational expressions are verified by numerical and analytical differentiation with respect to a static external electric field. Lastly, analytical gradients are further tested by performingmore » microcanonical excited state molecular dynamics with p-nitroaniline.« less

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

PubMed

Jung, Stephanie; Effelsberg, Uwe; Tallarek, Ulrich

2011-12-01

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

Solvent Exchange Leading to Nanobubble Nucleation: A Molecular Dynamics Study

PubMed Central

2017-01-01

The solvent exchange procedure has become the most-used protocol to produce surface nanobubbles, while the molecular mechanisms behind the solvent exchange are far from being fully understood. In this paper, we build a simple model and use molecular dynamics simulations to investigate the dynamic characteristics of solvent exchange for producing nanobubbles. We find that at the first stage of solvent exchange, there exists an interface between interchanging solvents of different gas solubility. This interface moves toward the substrate gradually as the exchange process proceeds. Our simulations reveal directed diffusion of gas molecules against the gas concentration gradient, driven by the solubility gradient of the liquid composition across the moving solvent–solvent interface. It is this directed diffusion that causes gas retention and produces a local gas oversaturation much higher near the substrate than far from it. At the second stage of solvent exchange, the high local gas oversaturation leads to bubble nucleation either on the solid surface or in the bulk solution, which is found to depend on the substrate hydrophobicity and the degree of local gas oversaturation. Our findings suggest that solvent exchange could be developed into a standard procedure to produce oversaturation and used to a variety of nucleation applications other than generating nanobubbles. PMID:28742364

Dip coating of sol-gels

NASA Astrophysics Data System (ADS)

Schunk, P. R.; Hurd, A. J.; Brinker, C. J.

Dip coating is the primary means of depositing sol-gel films for precision optical coatings. Sols are typically multicomponent systems consisting of an inorganic phase dispersed in a solvent mixture, with each component differing in volatility and surface tension. This, together with slow coating speeds (less than 1cm/s), makes analysis of the coating process complicated; unlike most high-speed coating methods, solvent evaporation, evolving rheology, and surface tension gradients alter significantly the fluid mechanics of the deposition stage. These phenomena were studied with computer-aided predictions of the flow and species transport fields. The underlying theory involves mass, momentum, and species transport on a domain of unknown shape, with models and constitutive equations for vapor-liquid equilibria and surface tension. Due accounting is made for the unknown position of the free surface, which locates according to the capillary hydrodynamic forces and solvent loss by evaporation. Predictions of the effects of mass transfer, hydrodynamics, and surface tension gradients on final film thickness are compared with ellipsometry measurements of film thickness on a laboratory pilot coater. Although quantitative agreement is still lacking, both experiment and theory reveal that the film profile near the drying line takes on a parabolic shape.

Porous fiber formation in polymer-solvent system undergoing solvent evaporation

NASA Astrophysics Data System (ADS)

Dayal, Pratyush; Kyu, Thein

2006-08-01

Temporal evolution of the fiber morphology during dry spinning has been investigated in the framework of Cahn-Hilliard equation [J. Chem. Phys. 28, 258 (1958)] pertaining to the concentration order parameter or volume fraction given by the Flory-Huggins free energy of mixing [P. J. Flory, Principles of Polymer Chemistry (Cornell University Press, Ithaca, NY, 1953), p. 672] in conjunction with the solvent evaporation rate. To guide the solvent evaporation induced phase separation, equilibrium phase diagram of the starting polymer solution was established on the basis of the Flory-Huggins free energy of mixing. The quasi-steady-state approximation has been adopted to account for the nonconserved nature of the concentration field caused by the solvent loss. The process of solvent evaporation across the fiber skin-air interface was treated in accordance with the classical Fick's law [R. B. Bird et al., Transport Phenomena (J. Wiley, New York, 1960), p. 780]. The simulated morphologies include gradient type, hollow fiber type, bicontinuous type, and host-guest type. The development of these diverse fiber morphologies is explicable in terms of the phase diagram of the polymer solution in a manner dependent on the competition between the phase separation dynamics and rate of solvent evaporation.

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

PubMed

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

2014-09-12

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

Optimal mixing rate in linear solvent strength gradient liquid chromatography. Balanced mixing program.

PubMed

Blumberg, Leonid M; Desmet, Gert

2016-12-09

The mixing rate (R ϕ ) is the temporal rate of increase in the solvent strength in gradient LC. The optimal R ϕ (R ϕ ,Opt ) is the one at which a required peak capacity of gradient LC analysis is obtained in the shortest time. The balanced mixing program is a one where, for better separation of early eluting solutes, the mixing ramp is preceded by a balanced isocratic hold of the duration depending on R ϕ . The improvement in the separation of the earlier eluites due to the balanced programming has been evaluated. The value of R ϕ ,Opt depends on the solvent composition range covered by the mixing ramp and on the column pressure conditions. The R ϕ ,Opt for a column operating at maximum instrumental pressure is different from R ϕ ,Opt for a column operating below the instrumental pressure limit. On the other hand, it has been shown that the difference in the R ϕ ,Opt values under different conditions is not very large so that a single default R ϕ previously recommended for gradient analyses without the isocratic hold also yields a good approximation to the shortest analysis time for all conditions in the balanced analyses. With or without the initial balance isocratic hold, the recommended default R ϕ is about 5%/t 0 (5% increase in the solvent strength per each t 0 -long increment in time) for small-molecule samples, and about an order of magnitude slower (0.5%/t 0 ) for protein samples. A discussion illustrating the use of the optimization criteria employed here for the techniques other than LSS gradient LC is included. Copyright © 2016 Elsevier B.V. All rights reserved.

Control of Evaporation Behavior of an Inkjet-Printed Dielectric Layer Using a Mixed-Solvent System

NASA Astrophysics Data System (ADS)

Yang, Hak Soon; Kang, Byung Ju; Oh, Je Hoon

2016-01-01

In this study, the evaporation behavior and the resulting morphology of inkjet-printed dielectric layers were controlled using a mixed-solvent system to fabricate uniform poly-4-vinylphenol (PVP) dielectric layers without any pinholes. The mixed-solvent system consisted of two different organic solvents: 1-hexanol and ethanol. The effects of inkjet-printing variables such as overlap condition, substrate temperature, and different printing sequences (continuous and interlacing printing methods) on the inkjet-printed dielectric layer were also investigated. Increasing volume fraction of ethanol (VFE) is likely to reduce the evaporation rate gradient and the drying time of the inkjet-printed dielectric layer; this diminishes the coffee stain effect and thereby improves the uniformity of the inkjet-printed dielectric layer. However, the coffee stain effect becomes more severe with an increase in the substrate temperature due to the enhanced outward convective flow. The overlap condition has little effect on the evaporation behavior of the printed dielectric layer. In addition, the interlacing printing method results in either a stronger coffee stain effect or wavy structures of the dielectric layers depending on the VFE of the PVP solution. All-inkjet-printed capacitors without electrical short circuiting can be successfully fabricated using the optimized PVP solution (VFE = 0.6); this indicates that the mixed-solvent system is expected to play an important role in the fabrication of high-quality inkjet-printed dielectric layers in various printed electronics applications.

Step-wise supercritical extraction of carbonaceous residua

DOEpatents

Warzinski, Robert P.

1987-01-01

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

Molecular Level Structure and Dynamics of Electrolytes Using 17O Nuclear Magnetic Resonance Spectroscopy

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

Murugesan, Vijayakumar; Han, Kee Sung; Hu, Jianzhi

2017-03-19

Electrolytes help harness the energy from electrochemical processes by serving as solvents and transport media for redox-active ions. Molecular-level interactions between ionic solutes and solvent molecules – commonly referred to as solvation phenomena – give rise to many functional properties of electrolytes such as ionic conductivity, viscosity, and stability. It is critical to understand the evolution of solvation phenomena as a function of competing counterions and solvent mixtures to predict and design the optimal electrolyte for a target application. Probing oxygen environments is of great interest as oxygens are located at strategic molecular sites in battery solvents and are directlymore » involved in inter- and intramolecular solvation interactions. NMR signals from 17O nuclei in battery electrolytes offer nondestructive bulk measurements of isotropic shielding, electric field gradient tensors, and transverse and longitudinal relaxation rates, which are excellent means for probing structure, bonding, and dynamics of both solute and solvent molecules. This article describes the use of 17O NMR spectroscopy in probing the solvation structures of various electrolyte systems ranging from transition metal ions in aqueous solution to lithium cations in organic solvent mixtures.« less

Phase-field approach to implicit solvation of biomolecules with Coulomb-field approximation

NASA Astrophysics Data System (ADS)

Zhao, Yanxiang; Kwan, Yuen-Yick; Che, Jianwei; Li, Bo; McCammon, J. Andrew

2013-07-01

A phase-field variational implicit-solvent approach is developed for the solvation of charged molecules. The starting point of such an approach is the representation of a solute-solvent interface by a phase field that takes one value in the solute region and another in the solvent region, with a smooth transition from one to the other on a small transition layer. The minimization of an effective free-energy functional of all possible phase fields determines the equilibrium conformations and free energies of an underlying molecular system. All the surface energy, the solute-solvent van der Waals interaction, and the electrostatic interaction are coupled together self-consistently through a phase field. The surface energy results from the minimization of a double-well potential and the gradient of a field. The electrostatic interaction is described by the Coulomb-field approximation. Accurate and efficient methods are designed and implemented to numerically relax an underlying charged molecular system. Applications to single ions, a two-plate system, and a two-domain protein reveal that the new theory and methods can capture capillary evaporation in hydrophobic confinement and corresponding multiple equilibrium states as found in molecular dynamics simulations. Comparisons of the phase-field and the original sharp-interface variational approaches are discussed.

Streamlined structure elucidation of an unknown compound in a pigment formulation.

PubMed

Yüce, Imanuel; Morlock, Gertrud E

2016-10-21

A fast and reliable quality control is important for ink manufacturers to ensure a constant production grade of mixtures and chemical formulations, and unknown components attract their attention. Structure elucidating techniques seem time-consuming in combination with column-based methods, but especially the low solubility of pigment formulations is challenging the analysis. In contrast, layer chromatography is more tolerant with regard to pigment particles. One PLC plate for NMR and FTIR analyses and one HPTLC plate for recording of high resolution mass spectra, MS/MS spectra and for gathering information on polarity and spectral properties were needed to characterize a structure, exemplarily shown for an unknown component in pigment Red 57:1 to be 3-hydroxy-2-naphtoic acid. A preparative layer chromatography (PLC) workflow was developed that used an Automated Multiple Development 2 (AMD 2) system. The 0.5-mm PLC plate could still be operated in the AMD 2 system and allowed a smooth switch from the analytical to the preparative gradient separation. Through automated gradient development and the resulting focusing of bands, the sharpness of the PLC bands was improved. For NMR, the necessary high load of the target compound on the PLC plate was achieved via a selective solvent extraction that discriminated the polar sample matrix and thus increased the application volume of the extract that could maximally be applied without overloading. By doing so, the yield for NMR analysis was improved by a factor of 9. The effectivity gain through a simple, but thoroughly chosen extraction solvent is often overlooked, and for educational purpose, it was clearly illustrated and demonstrated by an extended solvent screening. Thus, PLC using an automated gradient development after a selective extraction was proven to be a new powerful combination for structural elucidation by NMR. Copyright © 2016 Elsevier B.V. All rights reserved.

Transition-state optimization by the free energy gradient method: Application to aqueous-phase Menshutkin reaction between ammonia and methyl chloride

NASA Astrophysics Data System (ADS)

Hirao, Hajime; Nagae, Yukihiko; Nagaoka, Masataka

2001-11-01

The transition state (TS) for the Menshutkin reaction H 3N+CH 3Cl→H 3NCH 3++Cl - in aqueous solution was located on the free energy surface (FES) by the free energy gradient (FEG) method. The solute-solvent system was described by a hybrid quantum mechanical and molecular mechanical (QM/MM) method. The reaction path in water was found to deviate largely from that in the gas phase. It was concluded that, in such a reaction including charge separation, TS structure optimization on an FES is inevitable for obtaining valid information about a TS in solution.

Single fiber lignin distributions based on the density gradient column method

Treesearch

Brian Boyer; Alan W. Rudie

2007-01-01

The density gradient column method was used to determine the effects of uniform and non-uniform pulping processes on variation in individual fiber lignin concentrations of the resulting pulps. A density gradient column uses solvents of different densities and a mixing process to produce a column of liquid with a smooth transition from higher density at the bottom to...

Solvents and Parkinson disease: A systematic review of toxicological and epidemiological evidence

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

Lock, Edward A., E-mail: e.lock@ljmu.ac.uk; Zhang, Jing; Checkoway, Harvey

2013-02-01

Parkinson disease (PD) is a debilitating neurodegenerative motor disorder, with its motor symptoms largely attributable to loss of dopaminergic neurons in the substantia nigra. The causes of PD remain poorly understood, although environmental toxicants may play etiologic roles. Solvents are widespread neurotoxicants present in the workplace and ambient environment. Case reports of parkinsonism, including PD, have been associated with exposures to various solvents, most notably trichloroethylene (TCE). Animal toxicology studies have been conducted on various organic solvents, with some, including TCE, demonstrating potential for inducing nigral system damage. However, a confirmed animal model of solvent-induced PD has not been developed.more » Numerous epidemiologic studies have investigated potential links between solvents and PD, yielding mostly null or weak associations. An exception is a recent study of twins indicating possible etiologic relations with TCE and other chlorinated solvents, although findings were based on small numbers, and dose–response gradients were not observed. At present, there is no consistent evidence from either the toxicological or epidemiologic perspective that any specific solvent or class of solvents is a cause of PD. Future toxicological research that addresses mechanisms of nigral damage from TCE and its metabolites, with exposure routes and doses relevant to human exposures, is recommended. Improvements in epidemiologic research, especially with regard to quantitative characterization of long-term exposures to specific solvents, are needed to advance scientific knowledge on this topic. -- Highlights: ► The potential for organic solvents to cause Parkinson's disease has been reviewed. ► Twins study suggests etiologic relations with chlorinated solvents and Parkinson's. ► Animal studies with TCE showed potential to cause damage to dopaminergic neurons. ► Need to determine if effects in animals are relevant to human exposure levels.« less

Method and system for optical figuring by imagewise heating of a solvent

DOEpatents

Rushford, Michael C.

2005-08-30

A method and system of imagewise etching the surface of a substrate, such as thin glass, in a parallel process. The substrate surface is placed in contact with an etchant solution which increases in etch rate with temperature. A local thermal gradient is then generated in each of a plurality of selected local regions of a boundary layer of the etchant solution to imagewise etch the substrate surface in a parallel process. In one embodiment, the local thermal gradient is a local heating gradient produced at selected addresses chosen from an indexed array of addresses. The activation of each of the selected addresses is independently controlled by a computer processor so as to imagewise etch the substrate surface at region-specific etch rates. Moreover, etching progress is preferably concurrently monitored in real time over the entire surface area by an interferometer so as to deterministically control the computer processor to image-wise figure the substrate surface where needed.

Theory of Metastable State Relaxation in a Gravitational Field for Non-Critical Binary Systems with Non-Conserved Order Parameter

NASA Technical Reports Server (NTRS)

Izmailov, Alexander F.; Myerson, Allan S.

1993-01-01

A new mathematical ansatz is developed for solution of the time-dependent Ginzburg-Landau nonlinear partial differential equation describing metastable state relaxation in binary (solute+solvent) non-critical solutions with non-conserved scalar order parameter in presence of a gravitational field. It has been demonstrated analytically that in such systems metastability initiates heterogeneous solute redistribution which results in the formation of a non-equilibrium singly-periodic spatial solute structure in the new solute-rich phase. The critical radius of nucleation and the induction time in these systems are gravity-dependent. It has also been proved that metastable state relaxation in vertical columns of supersaturated non-critical binary solutions leads to formation of the solute concentration gradient. Analytical expression for this concentration gradient is found and analysed. It is concluded that gravity can initiate phase separation (nucleation or spinodal decomposition).

High-performance liquid chromatography with fluorescence detection for the rapid analysis of pheophytins and pyropheophytins in virgin olive oil.

PubMed

Li, Xueqi; Woodman, Michael; Wang, Selina C

2015-08-01

Pheophytins and pyropheophytin are degradation products of chlorophyll pigments, and their ratios can be used as a sensitive indicator of stress during the manufacturing and storage of olive oil. They increase over time depending on the storage condition and if the oil is exposed to heat treatments during the refining process. The traditional analysis method includes solvent- and time-consuming steps of solid-phase extraction followed by analysis by high-performance liquid chromatography with ultraviolet detection. We developed an improved dilute/fluorescence method where multi-step sample preparation was replaced by a simple isopropanol dilution before the high-performance liquid chromatography injection. A quaternary solvent gradient method was used to include a fourth strong solvent wash on a quaternary gradient pump, which avoided the need to premix any solvents and greatly reduced the oil residues on the column from previous analysis. This new method not only reduces analysis cost and time but shows reliability, repeatability, and improved sensitivity, especially important for low-level samples. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Solvent-programmed microchip open-channel electrochromatography.

PubMed

Kutter, J P; Jacobson, S C; Matsubara, N; Ramsey, J M

1998-08-01

Open-channel electrochromatography in combination with solvent programming is demonstrated using a microchip device. Channel walls were coated with octadecylsilanes at ambient temperatures, yielding stationary phases for chromatographic separations of neutral dyes. The electroosmotic flow after coating was sufficient to ensure transport of all species and on-chip mixing of isocratic and gradient elution conditions with acetonitrile-buffer mixtures. Chips having different channel depths between 10.2 and 2.9 μm were evaluated for performance, and van Deemter plots were established. Channel depths of about 5 μm were found to be a good compromise between efficiency and ease of operation. Isocratic and gradient elution conditions were easily established and manipulated by computer-controlled application of voltages to the terminals of the microchip. Linear gradients with different slopes, start times, duration times, and start percentages of organic modifier proved to be powerful tools to tune selectivity and analysis time for the separation of a test mixture. Even very steep gradients still produced excellent efficiencies. Together with fast reconditioning times, complete runs could be finished in under 60 s.

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

PubMed

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

2011-10-01

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

Chemotaxis of Molecular Dyes in Polymer Gradients in Solution.

PubMed

Guha, Rajarshi; Mohajerani, Farzad; Collins, Matthew; Ghosh, Subhadip; Sen, Ayusman; Velegol, Darrell

2017-11-08

Chemotaxis provides a mechanism for directing the transport of molecules along chemical gradients. Here, we show the chemotactic migration of dye molecules in response to the gradients of several different neutral polymers. The magnitude of chemotactic response depends on the structure of the monomer, polymer molecular weight and concentration, and the nature of the solvent. The mechanism involves cross-diffusion up the polymer gradient, driven by favorable dye-polymer interaction. Modeling allows us to quantitatively evaluate the strength of the interaction and the effect of the various parameters that govern chemotaxis.

Calixarene-Mediated Liquid-Membrane Transport of Choline Conjugates.

PubMed

Adhikari, Birendra Babu; Fujii, Ayu; Schramm, Michael P

2014-05-01

A series of supramolecular calixarenes efficiently transport distinct molecular species through a liquid membrane when attached to a receptor-complementary choline handle. Calix-[6]arene hexacarboxylic acid was highly effective at transporting different target molecules against a pH gradient. Both carboxylic- and phosphonic-acid-functionalized calix[4]arenes effect transport without requiring a pH or ion gradient. NMR binding studies, two-phase solvent extraction, and three-phase transport experiments reveal the necessary and subtle parameters to effect the transport of molecules attached to a choline "handle". On the other hand, rescorin[4]arene cavitands, which have similar guest recognition profiles, did not transport guest molecules. These developments reveal new approaches towards attempting synthetic-receptor-mediated selective small-molecule transport in vesicular and cellular systems.

Quantitative structure-retention relationships applied to development of liquid chromatography gradient-elution method for the separation of sartans.

PubMed

Golubović, Jelena; Protić, Ana; Otašević, Biljana; Zečević, Mira

2016-04-01

QSRR are mathematically derived relationships between the chromatographic parameters determined for a representative series of analytes in given separation systems and the molecular descriptors accounting for the structural differences among the investigated analytes. Artificial neural network is a technique of data analysis, which sets out to emulate the human brain's way of working. The aim of the present work was to optimize separation of six angiotensin receptor antagonists, so-called sartans: losartan, valsartan, irbesartan, telmisartan, candesartan cilexetil and eprosartan in a gradient-elution HPLC method. For this purpose, ANN as a mathematical tool was used for establishing a QSRR model based on molecular descriptors of sartans and varied instrumental conditions. The optimized model can be further used for prediction of an external congener of sartans and analysis of the influence of the analyte structure, represented through molecular descriptors, on retention behaviour. Molecular descriptors included in modelling were electrostatic, geometrical and quantum-chemical descriptors: connolly solvent excluded volume non-1,4 van der Waals energy, octanol/water distribution coefficient, polarizability, number of proton-donor sites and number of proton-acceptor sites. Varied instrumental conditions were gradient time, buffer pH and buffer molarity. High prediction ability of the optimized network enabled complete separation of the analytes within the run time of 15.5 min under following conditions: gradient time of 12.5 min, buffer pH of 3.95 and buffer molarity of 25 mM. Applied methodology showed the potential to predict retention behaviour of an external analyte with the properties within the training space. Connolly solvent excluded volume, polarizability and number of proton-acceptor sites appeared to be most influential paramateres on retention behaviour of the sartans. Copyright © 2015 Elsevier B.V. All rights reserved.

Are Water-lean Solvent Systems Viable for Post-Combustion CO 2 Capture?

DOE PAGES

Heldebrant, David J.; Koech, Phillip K.; Rousseau, Roger; ...

2017-08-18

Here, we present here an overview of water-lean solvents that compares their projected costs and performance to aqueous amine systems, emphasizing critical areas of study needed to evaluate their performance against their water-based brethren. The work presented her focuses on bridging these knowledge gaps. Because the majority of water-lean solvents are still at the lab scale, substantial studies are still needed to model their performance at scale. This presents a significant challenge as eachformulation has different physical and thermodynamic properties and behavior, and quantifying how these different properties manifest themselves in conventional absorber-stripper configurations, or identifying new configurations that aremore » specific for a solvent’s signature behavior. We identify critical areas of study that are needed, and our efforts (e.g. custom infrastructure, molecular models) to predict, measure, and model these behaviors. Such findings are critical for determining the rheology required for heat exchanger design; absorber designs and packing to accommodate solvents with gradient changes (e.g. viscosity, contact angle, surface tension), and stripper configurations without direct steam utilization or water reflux. Another critical area of research need is to understand the molecular structure of the liquid interface and bulk as a function of CO 2 loading, and to assess whether conventional film theories accurately quantify solvent behavior, or if thermodynamic models adequately quantify activity coefficients of ions in solution. We conclude with an assessment of our efforts to aid in bridging the knowledge gaps in understanding water-lean solvents, and suggestions of what is needed to enable large-scale demonstrations to meet the United States Department of Energy’s year 2030 goal.« less

Are Water-lean Solvent Systems Viable for Post-Combustion CO 2 Capture?

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

Heldebrant, David J.; Koech, Phillip K.; Rousseau, Roger

Here, we present here an overview of water-lean solvents that compares their projected costs and performance to aqueous amine systems, emphasizing critical areas of study needed to evaluate their performance against their water-based brethren. The work presented her focuses on bridging these knowledge gaps. Because the majority of water-lean solvents are still at the lab scale, substantial studies are still needed to model their performance at scale. This presents a significant challenge as eachformulation has different physical and thermodynamic properties and behavior, and quantifying how these different properties manifest themselves in conventional absorber-stripper configurations, or identifying new configurations that aremore » specific for a solvent’s signature behavior. We identify critical areas of study that are needed, and our efforts (e.g. custom infrastructure, molecular models) to predict, measure, and model these behaviors. Such findings are critical for determining the rheology required for heat exchanger design; absorber designs and packing to accommodate solvents with gradient changes (e.g. viscosity, contact angle, surface tension), and stripper configurations without direct steam utilization or water reflux. Another critical area of research need is to understand the molecular structure of the liquid interface and bulk as a function of CO 2 loading, and to assess whether conventional film theories accurately quantify solvent behavior, or if thermodynamic models adequately quantify activity coefficients of ions in solution. We conclude with an assessment of our efforts to aid in bridging the knowledge gaps in understanding water-lean solvents, and suggestions of what is needed to enable large-scale demonstrations to meet the United States Department of Energy’s year 2030 goal.« less

Accurate prediction of retention in hydrophilic interaction chromatography by back calculation of high pressure liquid chromatography gradient profiles.

PubMed

Wang, Nu; Boswell, Paul G

2017-10-20

Gradient retention times are difficult to project from the underlying retention factor (k) vs. solvent composition (φ) relationships. A major reason for this difficulty is that gradients produced by HPLC pumps are imperfect - gradient delay, gradient dispersion, and solvent mis-proportioning are all difficult to account for in calculations. However, we recently showed that a gradient "back-calculation" methodology can measure these imperfections and take them into account. In RPLC, when the back-calculation methodology was used, error in projected gradient retention times is as low as could be expected based on repeatability in the k vs. φ relationships. HILIC, however, presents a new challenge: the selectivity of HILIC columns drift strongly over time. Retention is repeatable in short time, but selectivity frequently drifts over the course of weeks. In this study, we set out to understand if the issue of selectivity drift can be avoid by doing our experiments quickly, and if there any other factors that make it difficult to predict gradient retention times from isocratic k vs. φ relationships when gradient imperfections are taken into account with the back-calculation methodology. While in past reports, the accuracy of retention projections was >5%, the back-calculation methodology brought our error down to ∼1%. This result was 6-43 times more accurate than projections made using ideal gradients and 3-5 times more accurate than the same retention projections made using offset gradients (i.e., gradients that only took gradient delay into account). Still, the error remained higher in our HILIC projections than in RPLC. Based on the shape of the back-calculated gradients, we suspect the higher error is a result of prominent gradient distortion caused by strong, preferential water uptake from the mobile phase into the stationary phase during the gradient - a factor our model did not properly take into account. It appears that, at least with the stationary phase we used, column distortion is an important factor to take into account in retention projection in HILIC that is not usually important in RPLC. Copyright © 2017 Elsevier B.V. All rights reserved.

Effects of liquid chromatography mobile phases and buffer salts on phosphorus inductively coupled plasma atomic emission and mass spectrometries utilizing ultrasonic nebulization and membrane desolvation.

PubMed

Carr, John E; Kwok, Kaho; Webster, Gregory K; Carnahan, Jon W

2006-01-23

Atomic spectrometry, specifically inductively coupled plasma atomic emission spectrometry (ICP-AES) and mass spectrometry (ICP-MS) show promise for heteroatom-based detection of pharmaceutical compounds. The combination of ultrasonic nebulization (USN) with membrane desolvation (MD) greatly enhances detection limits with these approaches. Because pharmaceutical analyses often incorporate liquid chromatography, the study herein was performed to examine the effects of solvent composition on the analytical behaviors of these approaches. The target analyte was phosphorus, introduced as phosphomycin. AES response was examined at the 253.7 nm atom line and mass 31 ions were monitored for the MS experiments. With pure aqueous solutions, detection limits of 5 ppb (0.5 ng in 0.1 mL injection volumes) were obtained with ICP-MS. The ICP-AES detection limit was 150 ppb. Solvent compositions were varied from 0 to 80% organic (acetonitrile and methanol) with nine buffers at concentrations typically used in liquid chromatography. In general, solvents and buffers had statistically significant, albeit small, effects on ICP-AES sensitivities. A few exceptions occurred in cases where typical liquid chromatography buffer concentrations produced higher mass loadings on the plasma. Indications are that isocratic separations can be reliably performed. Within reasonable accuracy tolerances, it appears that gradient chromatography can be performed without the need for signal response normalization. Organic solvent and buffer effects were more significant with ICP-MS. Sensitivities varied significantly with different buffers and organic solvent content. In these cases, gradient chromatography will require careful analytical calibration as solvent and buffer content is varied. However, for most buffer and solvent combinations, signal and detection limits are only moderately affected. Isocratic separations and detection are feasible.

Thermodynamic Paradigm for Solution Demixing Inspired by Nuclear Transport in Living Cells

NASA Astrophysics Data System (ADS)

Wang, Ching-Hao; Mehta, Pankaj; Elbaum, Michael

2017-04-01

Living cells display a remarkable capacity to compartmentalize their functional biochemistry. A particularly fascinating example is the cell nucleus. Exchange of macromolecules between the nucleus and the surrounding cytoplasm does not involve traversing a lipid bilayer membrane. Instead, large protein channels known as nuclear pores cross the nuclear envelope and regulate the passage of other proteins and RNA molecules. Beyond simply gating diffusion, the system of nuclear pores and associated transport receptors is able to generate substantial concentration gradients, at the energetic expense of guanosine triphosphate hydrolysis. In contrast to conventional approaches to demixing such as reverse osmosis and dialysis, the biological system operates continuously, without application of cyclic changes in pressure or solvent exchange. Abstracting the biological paradigm, we examine this transport system as a thermodynamic machine of solution demixing. Building on the construct of free energy transduction and biochemical kinetics, we find conditions for the stable operation and optimization of the concentration gradients as a function of dissipation in the form of entropy production.

Linearly scaling and almost Hamiltonian dielectric continuum molecular dynamics simulations through fast multipole expansions

NASA Astrophysics Data System (ADS)

Lorenzen, Konstantin; Mathias, Gerald; Tavan, Paul

2015-11-01

Hamiltonian Dielectric Solvent (HADES) is a recent method [S. Bauer et al., J. Chem. Phys. 140, 104103 (2014)] which enables atomistic Hamiltonian molecular dynamics (MD) simulations of peptides and proteins in dielectric solvent continua. Such simulations become rapidly impractical for large proteins, because the computational effort of HADES scales quadratically with the number N of atoms. If one tries to achieve linear scaling by applying a fast multipole method (FMM) to the computation of the HADES electrostatics, the Hamiltonian character (conservation of total energy, linear, and angular momenta) may get lost. Here, we show that the Hamiltonian character of HADES can be almost completely preserved, if the structure-adapted fast multipole method (SAMM) as recently redesigned by Lorenzen et al. [J. Chem. Theory Comput. 10, 3244-3259 (2014)] is suitably extended and is chosen as the FMM module. By this extension, the HADES/SAMM forces become exact gradients of the HADES/SAMM energy. Their translational and rotational invariance then guarantees (within the limits of numerical accuracy) the exact conservation of the linear and angular momenta. Also, the total energy is essentially conserved—up to residual algorithmic noise, which is caused by the periodically repeated SAMM interaction list updates. These updates entail very small temporal discontinuities of the force description, because the employed SAMM approximations represent deliberately balanced compromises between accuracy and efficiency. The energy-gradient corrected version of SAMM can also be applied, of course, to MD simulations of all-atom solvent-solute systems enclosed by periodic boundary conditions. However, as we demonstrate in passing, this choice does not offer any serious advantages.

Calixarene-Mediated Liquid-Membrane Transport of Choline Conjugates

PubMed Central

Adhikari, Birendra Babu; Fujii, Ayu

2015-01-01

A series of supramolecular calixarenes efficiently transport distinct molecular species through a liquid membrane when attached to a receptor-complementary choline handle. Calix-[6]arene hexacarboxylic acid was highly effective at transporting different target molecules against a pH gradient. Both carboxylic- and phosphonic-acid-functionalized calix[4]arenes effect transport without requiring a pH or ion gradient. NMR binding studies, two-phase solvent extraction, and three-phase transport experiments reveal the necessary and subtle parameters to effect the transport of molecules attached to a choline “handle”. On the other hand, rescorin[4]arene cavitands, which have similar guest recognition profiles, did not transport guest molecules. These developments reveal new approaches towards attempting synthetic-receptor-mediated selective small-molecule transport in vesicular and cellular systems. PMID:26161034

Thermal Motion and Forced Migration of Colloidal Particles Generate Hydrostatic Pressure in Solvent

PubMed Central

Hammel, H. T.; Scholander, P. F.

1973-01-01

A colloidal solution of ferrite particles in an osmometer has been used to demonstrate that the property that propels water across the semipermeable membrane is the decrease in hydrostatic pressure in the water of the solution. A magnetic field gradient directed so as to force the ferrite particles away from the semipermeable membrane of the osmometer and toward the free surface of the solution enhanced the colloidal osmotic pressure. The enhancement of this pressure was always exactly equal to the augmentation of the pressure as measured by the outward force of the particles, against the area of the free surface. Contrariwise, directing the magnetic field gradient so as to force the ferrite particles away from the free surface and toward the semipermeable membrane diminished the colloidal osmotic pressure of the solution. For a sufficiently forceful field gradient, the initial colloidal osmotic pressure could be negative, followed by an equilibrium pressure approaching zero regardless of the force of the particles against the membrane. Thus, the osmotic pressure of a solution is to be attributed to the pressure in the solvent generated in opposition to the pressure of the solute particles caused by their interaction with the free surface (Brownian motion and/or an external field force), or by their viscous shear when they migrate through the solvent, or both. PMID:16592046

Algorithms for Solvents and Spectral Factors of Matrix Polynomials

DTIC Science & Technology

1981-01-01

spectral factors of matrix polynomials LEANG S. SHIEHt, YIH T. TSAYt and NORMAN P. COLEMANt A generalized Newton method , based on the contracted gradient...of a matrix poly- nomial, is derived for solving the right (left) solvents and spectral factors of matrix polynomials. Two methods of selecting initial...estimates for rapid convergence of the newly developed numerical method are proposed. Also, new algorithms for solving complete sets of the right

Theoretical investigation of the weak interaction between graphene and alcohol solvents

NASA Astrophysics Data System (ADS)

Wang, Haining; Chen, Sian; Lu, Shanfu; Xiang, Yan

2017-05-01

The dispersion of graphene in five different alcohol solvents was investigated by evaluating the binding energy between graphene and alcohol molecules using DFT-D method. The calculation showed the most stable binding energy appeared at the distance of ∼3.5 Å between graphene and alcohol molecules and increased linearly as changing the alcohol from methanol to 1-pentanol. The weak interaction was further graphically illustrated using the reduced density gradient method. The theoretical study revealed alcohols with more carbon atoms could be a good starting point for screening suitable solvents for graphene dispersion.

Theoretical insight into the solvent effect of H2O and formamide on the cooperativity effect in HMX complex.

PubMed

Meng, Rui-Hong; Cao, Xiong; Hu, Shuang-Qi; Hu, Li-Shuang

2017-08-01

The cooperativity effects of the H-bonding interactions in HMX (1,3,5,7-tetranitro-1,3,5,7-tetrazacyclooctane)∙∙∙HMX∙∙∙FA (formamide), HMX∙∙∙HMX∙∙∙H 2 O and HMX∙∙∙HMX∙∙∙HMX complexes involving the chair and chair-chair HMX are investigated by using the ONIOM2 (CAM-B3LYP/6-31++G(d,p):PM3) and ONIOM2 (M06-2X/6-31++G(d,p):PM3) methods. The solvent effect of FA or H 2 O on the cooperativity effect in HMX∙∙∙HMX∙∙∙HMX are evaluated by the integral equation formalism polarized continuum model. The results show that the cooperativity and anti-cooperativity effects are not notable in all the systems. Although the effect of solvation on the binding energy of ternary system HMX∙∙∙HMX∙∙∙HMX is not large, that on the cooperativity of H-bonds is notable, which leads to the mutually strengthened H-bonding interaction in solution. This is perhaps the reason for the formation of different conformation of HMX in different solvent. Surface electrostatic potential and reduced density gradient are used to reveal the nature of the solvent effect on cooperativity effect in HMX∙∙∙HMX∙∙∙HMX. Graphical abstract RDG isosurface and electrostatic potential surface of HMX∙∙∙HMX∙∙∙HMX.

Electro-hydrodynamic spray synthesis and low temperature spectroscopic characterization of Perovskite thin films

NASA Astrophysics Data System (ADS)

Sarang, Som; Ishihara, Hidetaka; Tung, Vincent; Ghosh, Sayantani

Utilizing a Marangoni flow inspired electrospraying technique, we synthesize hybrid perovskite (PVSK) thin films with broad absorption spectrum and high crystallinity. The precursor solvents are electrosprayed onto an indium tin oxide (ITO) substrate, resulting in a gradient force developing between the droplet surface and the bulk due to the varying vapor pressure in the bi-solvent system. This gradient force helps the droplets propagate and merge with surrounding ones, forming a uniform thin film with excellent morphological and topological characteristics, as evident from the average power conversion efficiency (PCE) of 16%. In parallel, we use low temperature static and dynamic photoluminescence spectroscopy to probe the grain boundaries and defects in the synthesized PVSK thin films. At 120 K, the emergence of the low temperature orthorhombic phase is accompanied by reduction in lifetimes by an order of magnitude, a result attributed to charge transfer between the orthorhombic and tetragonal domains, as well as due to a crossover from free charge carrier to excitonic recombination. Our fabrication technique and optical studies help in advancement of PVSK based technology by providing unique insights into the fundamental physics of these novel materials. This research was supported by National Aeronautics and Space administration (NASA) Grant No: NNX15AQ01A.

Temperature gradient interaction chromatography of polymers: A molecular statistical model.

PubMed

Radke, Wolfgang; Lee, Sekyung; Chang, Taihyun

2010-11-01

A new model describing the retention in temperature gradient interaction chromatography of polymers is developed. The model predicts that polymers might elute in temperature gradient interaction chromatography in either an increasing or decreasing order or even nearly independent of molar mass, depending on the rate of the temperature increase relative to the flow rate. This is in contrast to solvent gradient elution, where polymers elute either in order of increasing molar mass or molar mass independent. The predictions of the newly developed model were verified with the literature data as well as new experimental data. Copyright © 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Suppression of Protonated Organic Solvents in NMR Spectroscopy Using a Perfect Echo Low-Pass Filtration Pulse Sequence.

PubMed

Howe, Peter W A

2018-04-03

Proton NMR spectra are usually acquired using deuterated solvents, but in many cases it is necessary to obtain spectra on samples in protonated solvents. In these cases, the intense resonances of the protonated solvents need to be suppressed to maximize sensitivity and spectral quality. A wide range of highly effective solvent suppression methods have been developed, but additional measures are needed to suppress the 13 C satellites of the solvent. Because the satellites represent 1.1% of the original solvent signal, they remain problematic if unsuppressed. The recently proposed DISPEL pulse sequences suppress 13 C satellites extremely effectively, and this Technical Note demonstrates that combining DISPEL and presaturation results in exceptionally effective solvent suppression. An important element in the effectiveness is volume selection, which is inherent within the DISPEL sequence. Spectra acquired in protonated dimethlysulfoxide and tetrahydrofuran show that optimum results are obtained by modifying the phase cycle, cycling the pulse-field gradients, and using broadband 13 C inversion pulses to reduce the effects of radiofrequency offset and inhomogeneity.

Some Peculiarities of Water Transport through Plasticized Nonporous Membranes

PubMed Central

Marian, S.; Jagur-Grodzinski, J.; Kedem, O.; Vofsi, D.

1970-01-01

“Liquid” and “plasticized” solvent membranes are of interest as possible analogues of biological systems. Semipermeable homogeneous films are prepared by plasticizing polyvinylchloride with organic phosphates. Water permeability of such films is relatively high. For a material containing 70% of 1.4-dihydroxyphenyl-bis(dibutylphosphate), the diffusion coefficient of water at room temperature was estimated to be about 1 × 10-6 cm2/sec. Conditioning of a plasticized membrane, under the osmotic gradient of solution of sodium nitrate, leads to profound changes in its morphology and to a drastic increase of its water permeability. The induced changes are reversible to a large extent. Their reversibility in various solutions may be correlated with the respective differences in permselectivity. The structure of expanded membranes and the mechanism of changes taking place under the osmotic gradients are discussed. ImagesFigure 2 PMID:5496907

Hanging drop crystal growth apparatus and method

NASA Technical Reports Server (NTRS)

Carter, Daniel C. (Inventor); Smith, Robbie E. (Inventor)

1989-01-01

An apparatus (10) is constructed having a cylindrical enclosure (16) within which a disc-shaped wicking element (18) is positioned. A well or recess (22) is cut into an upper side (24) of this wicking element, and a glass cover plate or slip (28) having a protein drop disposed thereon is sealably positioned on the wicking element (18), with drop (12) being positioned over well or recess (22). A flow of control fluid is generated by a programmable gradient former (16), with this control fluid having a vapor pressure that is selectively variable. This flow of control fluid is coupled to the wicking element (18) where control fluid vapor diffusing from walls (26) of the recess (22) is exposed to the drop (12), forming a vapor pressure gradient between the drop (12) and the control fluid vapor. Initially, this gradient is adjusted to draw solvent from the drop (12) at a relatively high rate, and as the critical supersaturation point is approached (the point at which crystal nucleation occurs), the gradient is reduced to more slowly draw solvent from the drop (12). This allows discrete protein molecules more time to orient themselves into an ordered crystalline lattice, producing protein crystals which, when processed by X-ray crystallography, possess a high degree of resolution.

Linearly scaling and almost Hamiltonian dielectric continuum molecular dynamics simulations through fast multipole expansions

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

Lorenzen, Konstantin; Mathias, Gerald; Tavan, Paul, E-mail: tavan@physik.uni-muenchen.de

2015-11-14

Hamiltonian Dielectric Solvent (HADES) is a recent method [S. Bauer et al., J. Chem. Phys. 140, 104103 (2014)] which enables atomistic Hamiltonian molecular dynamics (MD) simulations of peptides and proteins in dielectric solvent continua. Such simulations become rapidly impractical for large proteins, because the computational effort of HADES scales quadratically with the number N of atoms. If one tries to achieve linear scaling by applying a fast multipole method (FMM) to the computation of the HADES electrostatics, the Hamiltonian character (conservation of total energy, linear, and angular momenta) may get lost. Here, we show that the Hamiltonian character of HADESmore » can be almost completely preserved, if the structure-adapted fast multipole method (SAMM) as recently redesigned by Lorenzen et al. [J. Chem. Theory Comput. 10, 3244-3259 (2014)] is suitably extended and is chosen as the FMM module. By this extension, the HADES/SAMM forces become exact gradients of the HADES/SAMM energy. Their translational and rotational invariance then guarantees (within the limits of numerical accuracy) the exact conservation of the linear and angular momenta. Also, the total energy is essentially conserved—up to residual algorithmic noise, which is caused by the periodically repeated SAMM interaction list updates. These updates entail very small temporal discontinuities of the force description, because the employed SAMM approximations represent deliberately balanced compromises between accuracy and efficiency. The energy-gradient corrected version of SAMM can also be applied, of course, to MD simulations of all-atom solvent-solute systems enclosed by periodic boundary conditions. However, as we demonstrate in passing, this choice does not offer any serious advantages.« less

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

DOE PAGES

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

2016-06-04

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

Two tools for applying chromatographic retention data to the mass-based identification of peptides during hydrogen/deuterium exchange experiments by nano-liquid chromatography/matrix-assisted laser desorption/ionization mass spectrometry.

PubMed

Gershon, P D

2010-12-15

Two tools are described for integrating LC elution position with mass-based data in hydrogen-deuterium exchange (HDX) experiments by nano-liquid chromatography/matrix-assisted laser desorption/ionization mass spectrometry (nanoLC/MALDI-MS, a novel approach to HDX-MS). The first of these, 'TOF2H-Z Comparator', highlights peptides in HDX experiments that are potentially misidentified on the basis of mass alone. The program first calculates normalized values for the organic solvent concentration responsible for the elution of ions in nanoLC/MALDI HDX experiments. It then allows the solvent gradients for the multiple experiments contributing to an MS/MS-confirmed peptic peptide library to be brought into mutual alignment by iteratively re-modeling variables among LC parameters such as gradient shape, solvent species, fraction duration and LC dead time. Finally, using the program, high-probability chromatographic outliers can be flagged within HDX experimental data. The role of the second tool, 'TOF2H-XIC Comparator', is to normalize the LC chromatograms corresponding to all deuteration timepoints of all HDX experiments of a project, to a common reference. Accurate normalization facilitates the verification of chromatographic consistency between all ions whose spectral segments contribute to particular deuterium uptake plots. Gradient normalization in this manner revealed chromatographic inconsistencies between ions whose masses were either indistinguishable or separated by precise isotopic increments. Copyright © 2010 John Wiley & Sons, Ltd.

Tested Demonstrations.

ERIC Educational Resources Information Center

Gilbert, George L., Ed.

1985-01-01

Background information, procedures, and typical results obtained are provided for two demonstrations. The first involves the colorful complexes of copper(II). The second involves reverse-phase separation of Food, Drug, and Cosmetic (FD & C) dyes using a solvent gradient. (JN)

Simulation of elution profiles in liquid chromatography - II: Investigation of injection volume overload under gradient elution conditions applied to second dimension separations in two-dimensional liquid chromatography.

PubMed

Stoll, Dwight R; Sajulga, Ray W; Voigt, Bryan N; Larson, Eli J; Jeong, Lena N; Rutan, Sarah C

2017-11-10

An important research direction in the continued development of two-dimensional liquid chromatography (2D-LC) is to improve the detection sensitivity of the method. This is especially important in applications where injection of large volumes of effluent from the first dimension ( 1 D) column into the second dimension ( 2 D) column leads to severe 2 D peak broadening and peak shape distortion. For example, this is common when coupling two reversed-phase columns and the organic solvent content of the 1 D mobile phase overwhelms the 2 D column with each injection of 1 D effluent, leading to low resolution in the second dimension. In a previous study we validated a simulation approach based on the Craig distribution model and adapted from the work of Czok and Guiochon [1] that enabled accurate simulation of simple isocratic and gradient separations with very small injection volumes, and isocratic separations with mismatched injection and mobile phase solvents [2]. In the present study we have extended this simulation approach to simulate separations relevant to 2D-LC. Specifically, we have focused on simulating 2 D separations where gradient elution conditions are used, there is mismatch between the sample solvent and the starting point in the gradient elution program, injection volumes approach or even exceed the dead volume of the 2 D column, and the extent of sample loop filling is varied. To validate this simulation we have compared results from simulations and experiments for 101 different conditions, including variation in injection volume (0.4-80μL), loop filling level (25-100%), and degree of mismatch between sample organic solvent and the starting point in the gradient elution program (-20 to +20% ACN). We find that that the simulation is accurate enough (median errors in retention time and peak width of -1.0 and -4.9%, without corrections for extra-column dispersion) to be useful in guiding optimization of 2D-LC separations. However, this requires that real injection profiles obtained from 2D-LC interface valves are used to simulate the introduction of samples into the 2 D column. These profiles are highly asymmetric - simulation using simple rectangular pulses leads to peak widths that are far too narrow under many conditions. We believe the simulation approach developed here will be useful for addressing practical questions in the development of 2D-LC methods. Copyright © 2017 Elsevier B.V. All rights reserved.

Bioinspired Programmable Polymer Gel Controlled by Swellable Guest Medium.

PubMed

Deng, Heng; Dong, Yuan; Su, Jheng-Wun; Zhang, Cheng; Xie, Yunchao; Zhang, Chi; Maschmann, Matthew R; Lin, Yuyi; Lin, Jian

2017-09-13

Responsive materials with functions of forming three-dimensional (3D) origami and/or kirigami structures have a broad range of applications in bioelectronics, metamaterials, microrobotics, and microelectromechanical (MEMS) systems. To realize such functions, building blocks of actuating components usually possess localized inhomogeneity so that they respond differently to external stimuli. Previous fabrication strategies lie in localizing nonswellable or less-swellable guest components in their swellable host polymers to reduce swelling ability. Herein, inspired by ice plant seed capsules, we report an opposite strategy of implanting swellable guest medium inside nonswellable host polymers to locally enhance the swelling inhomogeneity. Specifically, we adopted a skinning effect induced surface polymerization combined with direct laser writing to control gradient of swellable cyclopentanone (CP) in both vertical and lateral directions of the nonswellable SU-8. For the first time, the laser direct writing was used as a novel strategy for patterning programmable polymer gel films. Upon stimulation of organic solvents, the dual-gradient gel films designed by origami or kirigami principles exhibit reversible 3D shape transformation. Molecular dynamics (MD) simulation illustrates that CP greatly enhances diffusion rates of stimulus solvent molecules in the SU-8 matrix, which offers the driving force for the programmable response. Furthermore, this bioinspired strategy offers unique capabilities in fabricating responsive devices such as a soft gripper and a locomotive robot, paving new routes to many other responsive polymers.

Microwave- and ultrasound-assisted extraction of vanillin and its quantification by high-performance liquid chromatography in Vanilla planifolia.

PubMed

Sharma, Anuj; Verma, Subash Chandra; Saxena, Nisha; Chadda, Neetu; Singh, Narendra Pratap; Sinha, Arun Kumar

2006-03-01

Microwave-assisted extraction (MAE), ultrasound-assisted extraction (UAE) and conventional extraction of vanillin and its quantification by HPLC in pods of Vanilla planifolia is described. A range of nonpolar to polar solvents were used for the extraction of vanillin employing MAE, UAE and conventional methods. Various extraction parameters such as nature of the solvent, solvent volume, time of irradiation, microwave and ultrasound energy inputs were optimized. HPLC was performed on RP ODS column (4.6 mm ID x 250 mm, 5 microm, Waters), a photodiode array detector (Waters 2996) using gradient solvent system of ACN and ortho-phosphoric acid in water (0.001:99.999 v/v) at 25 degrees C. Regression equation revealed a linear relationship (r2 > 0.9998) between the mass of vanillin injected and the peak areas. The detection limit (S/N = 3) and limit of quantification (S/N = 10) were 0.65 and 1.2 microg/g, respectively. Recovery was achieved in the range 98.5-99.6% for vanillin. Maximum yield of vanilla extract (29.81, 29.068 and 14.31% by conventional extraction, MAE and UAE, respectively) was found in a mixture of ethanol/water (40:60 v/v). Dehydrated ethanolic extract showed the highest amount of vanillin (1.8, 1.25 and 0.99% by MAE, conventional extraction and UAE, respectively).

Evaluation of 1.0 mm i.d. column performances on ultra high pressure liquid chromatography instrumentation.

PubMed

Lestremau, François; Wu, Di; Szücs, Roman

2010-07-23

The present study focuses on the evaluation of 1.0 mm i.d. (internal diameter) columns on a commercial Ultra-High Pressure system. These systems have been developed specifically to operate columns with small volumes, typically 2.1 mm i.d., by reducing extra-column volume dispersion. The use of columns with smaller i.d. results in a reduced solvent consumption and required sample volume. The evaluation of the columns was carried out with samples containing neutral and pharmaceutical compounds. In isocratic mode, the extra-column volume produced additional band broadening leading to poor performances compared to equivalent 2.1 mm i.d. columns. By increasing the length of the column, the influence of the extra-column bandspreading could be reduced and 75,000 plates were obtained when four columns were coupled. In gradient mode, the effect of the extra-column contribution on efficiency was limited and about 80% of the performance of the 2.1 mm i.d. columns was obtained. Optimum conditions in gradient mode were further investigated by changing flow rate, gradient time and column length. A different approach of the calculation of peak capacity was also considered for the comparison of the influence of these different parameters. Copyright (c) 2010 Elsevier B.V. All rights reserved.

Reversed-phase high-performance liquid chromatographic method for the determination of peptidoglycan monomers and structurally related peptides and adamantyltripeptides.

PubMed

Krstanović, Marina; Frkanec, Ruza; Vranesić, Branka; Ljevaković, Durdica; Sporec, Vesna; Tomasić, Jelka

2002-06-25

The reversed-phase HPLC method using UV detection was developed for the determination of (a) immunostimulating peptidoglycan monomers represented by the basic structure GlcNAc-MurNAc-L-Ala-D-isoGln-meso-DAP(omegaNH(2))-D-Ala-D-Ala (PGM) and two more lipophilic derivatives, Boc-Tyr-PGM and (Ada-1-yl)-CH(2)-CO-PGM, (b) two diastereomeric immunostimulating adamantyltripeptides L- and D-(adamant-2-yl)-Gly-L-Ala-D-isoGln and (c) peptides obtained by the enzyme hydrolyses of peptidoglycans and related peptides. The enzymes used, N-acetylmuramyl-L-alanine amidase and an L,D-aminopeptidase are present in mammalian sera and are involved in the metabolism of peptidoglycans and related peptides. Appropriate solvent systems were chosen with regard to structure and lipophilicity of each compound. As well, different gradient systems within the same solvent system had to be applied in order to achieve satisfactory separation and retention time. HPLC separation was developed with the aim to use this method for the study of the stability of the tested compounds, the purity during preparation and isolation and for following the enzyme hydrolyses.

Solid-state diode-like chemiluminescence based on serial, immobilized concentration gradients in mixed-valent poly[Ru(vbpy){sub 3}](PF{sub 6}){sub 2} films

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

Maness, K.M.; Terrill, R.H.; Meyer, T.J.

The electronic conductivity and electrogenerated chemiluminescence (ECL) of thin, electropolymerized films of the fixed-site redox polymer poly[Ru(vbpy){sub 3}](PF{sub 6}){sub 2} (vbpy = 4-vinyl-4`-methyl-2,2`-bipyridine) on Pt interdigitated array electrodes were examined for both solvent-swollen and dry films. In both cases emission arose from {sup *}Ru{sup 2+} produced via the electron-transfer reaction between Ru{sup 3+} and Ru{sup 1+} states within the film (Ru = Ru-(vbpy){sub 3}). Dry films contained fixed concentration gradients of Ru{sup 3+}, Ru{sup 2+}, and Ru{sup 1+} states which were first introduced in an acetonitrile-swollen film via the constant potential oxidation and reduction of Ru{sup 2+} at opposing IDAmore » fingers. The gradients were then immobilized by drying and cooling the film while retaining the inter-electrode bias (2.6V). The resulting dried and cooled films responded rapidly to changes in voltage bias and exhibited diode-like characteristics, conducting and emitting light at biases >2.6 V and undergoing a reverse bias breakdown current, unassociated with light emission, at ca. -5.5 V. At 0{degree}C the optimum quantum efficiency of solid-state ECL emission ({phi}{sub ECL}) was similar to that in solvent-swollen films: 0.0003 photon/electron. In contrast to the dry films, solvent-swollen films were slow to respond to changes in voltage bias and did not exhibit diode-like behavior. 18 refs., 7 figs.« less

A systematic investigation of sample diluents in modern supercritical fluid chromatography.

PubMed

Desfontaine, Vincent; Tarafder, Abhijit; Hill, Jason; Fairchild, Jacob; Grand-Guillaume Perrenoud, Alexandre; Veuthey, Jean-Luc; Guillarme, Davy

2017-08-18

This paper focuses on the possibility to inject large volumes (up to 10μL) in ultra-high performance supercritical fluid chromatography (UHPSFC) under generic gradient conditions. Several injection and method parameters have been individually evaluated (i.e. analyte concentration, injection volume, initial percentage of co-solvent in the gradient, nature of the weak needle wash solvent, nature of the sample diluent, nature of the column and of the analyte). The most critical parameters were further investigated using in a multivariate approach. The overall results suggested that several aprotic solvents including methyl tert-butyl ether (MTBE), dichloromethane, acetonitrile or cyclopentyl methyl ether (CPME) were well adapted for the injection of large volume in UHPSFC, while MeOH was generally the worst alternative. However, the nature of the stationary phase also had a strong impact and some of these diluents did not perform equally on each column. This was due to the existence of a competition in the adsorption of the analyte and the diluent on the stationary phase. This observation introduced the idea that the sample diluent should not only be chosen according to the analyte but also to the column chemistry to limit the interactions between the diluent and the ligands. Other important characteristics of the "ideal" SFC sample diluent were finally highlighted. Aprotic solvents with low viscosity are preferable to avoid strong solvent effects and viscous fingering, respectively. In the end, the authors suggest that the choice of the sample diluent should be part of the method development, as a function of the analyte and the selected stationary phase. Copyright © 2017 Elsevier B.V. All rights reserved.

Development and validation of a headspace gas chromatographic method for the determination of residual solvents in arterolane (RBx11160) maleate bulk drug

PubMed Central

Gupta, Abhishek; Singh, Yogendra; Srinivas, Kona S.; Jain, Garima; Sreekumar, V. B.; Semwal, Vinod Prasad

2010-01-01

Objective: Arterolane maleate is an antimalarial drug currently under Phase III clinical evaluation, and presents a simple, economical and scalable synthesis, and does not suffer from safety problems. Arterolane maleate is more active than artemisinin; and is cheap to produce. It has a longer lifetime in the plasma, so it stays active longer in the body. To provide quality control over the manufacture of any API, it is essential to develop highly selective analytical methods. In the current article we are reporting the development and validation of a rapid and specific Head space gas chromatographic (HSGC) method for the determination of organic volatile impurities (residual solvents) in Arterolane Maleate bulk drug. Materials and Methods: The method development and its validation were performed on Perkin Elmer's gas chromatographic system equipped with Flame Ionization detector and head space analyzer. The method involved a thermal gradient elution of ten residual solvents present in arterolane maleate salt in RTx-624, 30 m × 0.32 mm, 1.8 μ column using nitrogen gas as a carrier. The flow rate was 0.5 ml/min and flame ionization detector (FID) was used. Results: During method validation, parameters such as precision, linearity, accuracy, limit of quantification and detection and specificity were evaluated, which remained within acceptable limits. Conclusions: The method has been successfully applied for the quantification of the amount of residual solvents present in arterolane maleate bulk drug.The method presents a simple and reliable solution for the routine quantitative analysis of residual solvents in Arterolane maleate bulk drug. PMID:21814428

Photodegradation of dioxin in contaminated soil in the presence of solvents and nanoscale TiO2 particles.

PubMed

Binh, Nguyen Duy; Oanh, Nguyen Thi Kim; Parkpian, Preeda

2014-01-01

Decomposition of 2,3,7,8-Tetrachlorodibenzo-p-dioxin (2,3,7,8-TCDD) present in soil under ultraviolet (UV) illumination (350-400nm) was investigated using a combination of nontoxic solvents mixed in soil and nanoscale anatase TiO2 (nTiO2) distributed on 2mm top soil surface. Three types of UV-exposure experiments were conducted: intermittent exposure (8 h/day) for 90 days and 120 days, sequential intermittent (120 days) and continuous (24 h/day) for the next 55 days, and continuous exposure for 55 days. The influence of several factors on dioxin photodegradation efficiency was investigated, including the UV absorption by the targeted dioxin, presence of catalytic nTiO2 on soil surface, solvent evaporation rate, as well as vertical gradients of solvents added into the soil columns. Results of dioxin analysis for the soil samples collected at the end of every experiment condition show that the photodegradation enhanced by the nTiO2 presence on the soil surface considerably increased the dioxin removal. Higher removal efficiencies were found for treatments with 15%wt of nTiO2 mixed in the 2-mm surface soil as compared to the 5%wt nTiO2 treatments. The highest removal efficiency (79.6%) was for the sequential intermittent-continuous UV-exposure experiment with nTiO2. Dechlorinated products of 2,3,7,8-TCDD were generally not detected which suggests degradation of targeted dioxin by C-Cl cleavage was negligible. Further modifications to improve removal efficiencies were proposed. Large-scale engineered systems may employ this integrated treatment approach which can also incorporate the reuse of the top soil containing nTiO2 and solvent vapours. With the utilization of natural sunlight such systems would be promisingly suitable for tropical conditions.

Microfluidic chip for peptide analysis with an integrated HPLC column, sample enrichment column, and nanoelectrospray tip.

PubMed

Yin, Hongfeng; Killeen, Kevin; Brennen, Reid; Sobek, Dan; Werlich, Mark; van de Goor, Tom

2005-01-15

Current nano-LC/MS systems require the use of an enrichment column, a separation column, a nanospray tip, and the fittings needed to connect these parts together. In this paper, we present a microfabricated approach to nano-LC, which integrates these components on a single LC chip, eliminating the need for conventional LC connections. The chip was fabricated by laminating polyimide films with laser-ablated channels, ports, and frit structures. The enrichment and separation columns were packed using conventional reversed-phase chromatography particles. A face-seal rotary valve provided a means for switching between sample loading and separation configurations with minimum dead and delay volumes while allowing high-pressure operation. The LC chip and valve assembly were mounted within a custom electrospray source on an ion-trap mass spectrometer. The overall system performance was demonstrated through reversed-phase gradient separations of tryptic protein digests at flow rates between 100 and 400 nL/min. Microfluidic integration of the nano-LC components enabled separations with subfemtomole detection sensitivity, minimal carryover, and robust and stable electrospray throughout the LC solvent gradient.

An instant multi-responsive porous polymer actuator driven by solvent molecule sorption.

PubMed

Zhao, Qiang; Dunlop, John W C; Qiu, Xunlin; Huang, Feihe; Zhang, Zibin; Heyda, Jan; Dzubiella, Joachim; Antonietti, Markus; Yuan, Jiayin

2014-07-01

Fast actuation speed, large-shape deformation and robust responsiveness are critical to synthetic soft actuators. A simultaneous optimization of all these aspects without trade-offs remains unresolved. Here we describe porous polymer actuators that bend in response to acetone vapour (24 kPa, 20 °C) at a speed of an order of magnitude faster than the state-of-the-art, coupled with a large-scale locomotion. They are meanwhile multi-responsive towards a variety of organic vapours in both the dry and wet states, thus distinctive from the traditional gel actuation systems that become inactive when dried. The actuator is easy-to-make and survives even after hydrothermal processing (200 °C, 24 h) and pressing-pressure (100 MPa) treatments. In addition, the beneficial responsiveness is transferable, being able to turn 'inert' objects into actuators through surface coating. This advanced actuator arises from the unique combination of porous morphology, gradient structure and the interaction between solvent molecules and actuator materials.

Systemic study of solvent-assisted active loading of gambogic acid into liposomes and its formulation optimization for improved delivery.

PubMed

Tang, Wei-Lun; Tang, Wei-Hsin; Szeitz, Andras; Kulkarni, Jayesh; Cullis, Pieter; Li, Shyh-Dar

2018-06-01

The solvent-assisted active loading technology (SALT) was developed for encapsulating a water insoluble weak base into the liposomal core in the presence of 5% DMSO. In this study, we further examined the effect of various water miscible solvents in promoting active loading of other types of drugs into liposomes. To achieve complete drug loading, the amount of solvent required must result in complete drug solubilization and membrane permeability enhancement, but must be below the threshold that induces liposomal aggregation or causes bilayer disruption. We then used the SALT to load gambogic acid (GA, an insoluble model drug that shows promising anticancer effect) into liposomes, and optimized the loading gradient and lipid composition to prepare a stable formulation (Lipo-GA) that displayed >95% drug retention after incubation with serum for 3 days. Lipo-GA contained a high drug-to-lipid ratio of 1/5 (w/w) with a mean particle size of ∼75 nm. It also displayed a prolonged circulation half-life (1.5 h vs. 18.6 h) and enhanced antitumor activity in two syngeneic mice models compared to free GA. Particularly, complete tumor regression was observed in the EMT6 tumor model for 14 d with significant inhibition of multiple oncogenes including HIF-1α, VEGF-A, STAT3, BCL-2, and NF-κB. Copyright © 2018 Elsevier Ltd. All rights reserved.

HPLC Determination of Esculin and Esculetin in Rat Plasma for Pharmacokinetic Studies.

PubMed

Rehman, Shaheed Ur; Kim, In Sook; Kang, Ki Sung; Yoo, Hye Hyun

2015-09-01

An optimized, sensitive and validated reversed-phase high-performance liquid chromatography (RP-HPLC) method with UV detection is described for simultaneous determination of esculin and its aglycone, esculetin, in rat plasma. After addition of internal standard (chrysin), plasma samples were pretreated by solid-phase extraction and introduced into the HPLC system. Analytes were separated on a RP C18 column with a mobile phase of 0.075% acetic acid in water (solvent A) and 90% acetonitrile in solvent A (solvent B) using gradient elution at a flow rate of 1.0 mL/min. The wavelength for UV detection was set at 338 nm. Calibration curves for esculin and esculetin were constructed over a range of 10-1,000 ng/mL. The developed method was found to be specific, precise and accurate. The method was successfully applied to study the pharmacokinetics of esculin and esculetin in rats. After oral administration of 120 mg/kg, the mean Cmax values were 340.3 and 316.5 ng/mL and the AUClast values were 377.3 and 1276.5 h ng/mL for esculin and esculetin, respectively. The bioavailability of esculin was calculated to be 0.62%. © The Author 2015. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

Ionic conduction and self-diffusion near infinitesimal concentration in lithium salt-organic solvent electrolytes

NASA Astrophysics Data System (ADS)

Aihara, Yuichi; Sugimoto, Kyoko; Price, William S.; Hayamizu, Kikuko

2000-08-01

The Debye-Hückel-Onsager and Nernst-Einstein equations, which are based on two different conceptual approaches, constitute the most widely used equations for relating ionic conduction to ionic mobility. However, both of these classical (simple) equations are predictive of ionic conductivity only at very low salt concentrations. In the present work the ionic conductivity of four organic solvent-lithium salt-based electrolytes were measured. These experimental conductivity values were then contrasted with theoretical values calculated using the translational diffusion (also known as self-diffusion or intradiffusion) coefficients of all of the species present obtained using pulsed-gradient spin-echo (1H, 19F and 7Li) nuclear magnetic resonance self-diffusion measurements. The experimental results verified the applicability of both theoretical approaches at very low salt concentrations for these particular systems as well as helping to clarify the reasons for the divergence between theory and experiment. In particular, it was found that the correspondence between the Debye-Hückel-Onsager equation and experimental values could be improved by using the measured solvent self-diffusion values to correct for salt-induced changes in the solution viscosity. The concentration dependence of the self-diffusion coefficients is discussed in terms of the Jones-Dole equation.

Optimization of non-linear gradient in hydrophobic interaction chromatography for the analytical characterization of antibody-drug conjugates.

PubMed

Bobály, Balázs; Randazzo, Giuseppe Marco; Rudaz, Serge; Guillarme, Davy; Fekete, Szabolcs

2017-01-20

The goal of this work was to evaluate the potential of non-linear gradients in hydrophobic interaction chromatography (HIC), to improve the separation between the different homologous species (drug-to-antibody, DAR) of commercial antibody-drug conjugates (ADC). The selectivities between Brentuximab Vedotin species were measured using three different gradient profiles, namely linear, power function based and logarithmic ones. The logarithmic gradient provides the most equidistant retention distribution for the DAR species and offers the best overall separation of cysteine linked ADC in HIC. Another important advantage of the logarithmic gradient, is its peak focusing effect for the DAR0 species, which is particularly useful to improve the quantitation limit of DAR0. Finally, the logarithmic behavior of DAR species of ADC in HIC was modelled using two different approaches, based on i) the linear solvent strength theory (LSS) and two scouting linear gradients and ii) a new derived equation and two logarithmic scouting gradients. In both cases, the retention predictions were excellent and systematically below 3% compared to the experimental values. Copyright © 2016 Elsevier B.V. All rights reserved.

Solvation behavior of carbonate-based electrolytes in sodium ion batteries.

PubMed

Cresce, Arthur V; Russell, Selena M; Borodin, Oleg; Allen, Joshua A; Schroeder, Marshall A; Dai, Michael; Peng, Jing; Gobet, Mallory P; Greenbaum, Steven G; Rogers, Reginald E; Xu, Kang

2016-12-21

Sodium ion batteries are on the cusp of being a commercially available technology. Compared to lithium ion batteries, sodium ion batteries can potentially offer an attractive dollar-per-kilowatt-hour value, though at the penalty of reduced energy density. As a materials system, sodium ion batteries present a unique opportunity to apply lessons learned in the study of electrolytes for lithium ion batteries; specifically, the behavior of the sodium ion in an organic carbonate solution and the relationship of ion solvation with electrode surface passivation. In this work the Li + and Na + -based solvates were characterized using electrospray mass spectrometry, infrared and Raman spectroscopy, 17 O, 23 Na and pulse field gradient double-stimulated-echo pulse sequence nuclear magnetic resonance (NMR), and conductivity measurements. Spectroscopic evidence demonstrate that the Li + and Na + cations share a number of similar ion-solvent interaction trends, such as a preference in the gas and liquid phase for a solvation shell rich in cyclic carbonates over linear carbonates and fluorinated carbonates. However, quite different IR spectra due to the PF 6 - anion interactions with the Na + and Li + cations were observed and were rationalized with the help of density functional theory (DFT) calculations that were also used to examine the relative free energies of solvates using cluster - continuum models. Ion-solvent distances for Na + were longer than Li + , and Na + had a greater tendency towards forming contact pairs compared to Li + in linear carbonate solvents. In tests of hard carbon Na-ion batteries, performance was not well correlated to Na + solvent preference, leading to the possibility that Na + solvent preference may play a reduced role in the passivation of anode surfaces and overall Na-ion battery performance.

An electrochemical pumping system for on-chip gradient generation.

PubMed

Xie, Jun; Miao, Yunan; Shih, Jason; He, Qing; Liu, Jun; Tai, Yu-Chong; Lee, Terry D

2004-07-01

Within the context of microfluidic systems, it has been difficult to devise pumping systems that can deliver adequate flow rates at high pressure for applications such as HPLC. An on-chip electrochemical pumping system based on electrolysis that offers certain advantages over designs that utilize electroosmotic driven flow has been fabricated and tested. The pump was fabricated on both silicon and glass substrates using photolithography. The electrolysis electrodes were formed from either platinum or gold, and SU8, an epoxy-based photoresist, was used to form the pump chambers. A glass cover plate and a poly(dimethylsiloxane) (PDMS) gasket were used to seal the chambers. Filling of the chambers was accomplished by using a syringe to inject liquid via filling ports, which were later sealed using a glass cover plate. The current supplied to the electrodes controlled the rate of gas formation and, thus, the resulting fluid flow rate. At low backpressures, flow rates >1 microL/min have been demonstrated using <1 mW of power. Pumping at backpressures as high as 200 psi have been demonstrated, with 20 nL/min having been observed using <4 mW. By integrating two electrochemical pumps with a polymer electrospray nozzle, we have confirmed the successful generation of a solvent gradient via a mass spectrometer.

Efficient minimization of multipole electrostatic potentials in torsion space

PubMed Central

Bodmer, Nicholas K.

2018-01-01

The development of models of macromolecular electrostatics capable of delivering improved fidelity to quantum mechanical calculations is an active field of research in computational chemistry. Most molecular force field development takes place in the context of models with full Cartesian coordinate degrees of freedom. Nevertheless, a number of macromolecular modeling programs use a reduced set of conformational variables limited to rotatable bonds. Efficient algorithms for minimizing the energies of macromolecular systems with torsional degrees of freedom have been developed with the assumption that all atom-atom interaction potentials are isotropic. We describe novel modifications to address the anisotropy of higher order multipole terms while retaining the efficiency of these approaches. In addition, we present a treatment for obtaining derivatives of atom-centered tensors with respect to torsional degrees of freedom. We apply these results to enable minimization of the Amoeba multipole electrostatics potential in a system with torsional degrees of freedom, and validate the correctness of the gradients by comparison to finite difference approximations. In the interest of enabling a complete model of electrostatics with implicit treatment of solvent-mediated effects, we also derive expressions for the derivative of solvent accessible surface area with respect to torsional degrees of freedom. PMID:29641557

Separation of five compounds from leaves of Andrographis paniculata (Burm. f.) Nees by off-line two-dimensional high-speed counter-current chromatography combined with gradient and recycling elution.

PubMed

Zhang, Li; Liu, Qi; Yu, Jingang; Zeng, Hualiang; Jiang, Shujing; Chen, Xiaoqing

2015-05-01

An off-line two-dimensional high-speed counter-current chromatography method combined with gradient and recycling elution mode was established to isolate terpenoids and flavones from the leaves of Andrographis paniculata (Burm. f.) Nees. By using the solvent systems composed of n-hexane/ethyl acetate/methanol/water with different volume ratios, five compounds including roseooside, 5,4'-dihydroxyflavonoid-7-O-β-d-pyranglucuronatebutylester, 7,8-dimethoxy-2'-hydroxy-5-O-β-d-glucopyranosyloxyflavon, 14-deoxyandrographiside, and andrographolide were successfully isolated. Purities of these isolated compounds were all over 95% as determined by high-performance liquid chromatography. Their structures were identified by UV, mass spectrometry, and (1) H NMR spectroscopy. It has been demonstrated that the combination of off-line two-dimensional high-speed counter-current chromatography with different elution modes is an efficient technique to isolate compounds from complex natural product extracts. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Quantifying the loss of methane through secondary gas mass transport (or 'slip') from a micro-porous membrane contactor applied to biogas upgrading.

PubMed

McLeod, Andrew; Jefferson, Bruce; McAdam, Ewan J

2013-07-01

Secondary gas transport during the separation of a binary gas with a micro-porous hollow fibre membrane contactor (HMFC) has been studied for biogas upgrading. In this application, the loss or 'slip' of the secondary gas (methane) during separation is a known concern, specifically since methane possesses the intrinsic calorific value. Deionised (DI) water was initially used as the physical solvent. Under these conditions, carbon dioxide (CO2) and methane (CH4) absorption were dependent upon liquid velocity (V(L)). Whilst the highest CO2 flux was recorded at high V(L), selectivity towards CO2 declined due to low residence times and a diminished gas-side partial pressure, and resulted in slip of approximately 5.2% of the inlet methane. Sodium hydroxide was subsequently used as a comparative chemical absorption solvent. Under these conditions, CO2 mass transfer increased by increasing gas velocity (VG) which is attributed to the excess of reactive hydroxide ions present in the solvent, and the fast conversion of dissolved CO2 to carbonate species reinitiating the concentration gradient at the gas-liquid interface. At high gas velocities, CH4 slip was reduced to 0.1% under chemical conditions. Methane slip is therefore dependent upon whether the process is gas phase or liquid phase controlled, since methane mass transport can be adequately described by Henry's law within both physical and chemical solvents. The addition of an electrolyte was found to further retard CH4 absorption via the salting out effect. However, their applicability to physical solvents is limited since electrolytic concentration similarly impinges upon the solvents' capacity for CO2. This study illustrates the significance of secondary gas mass transport, and furthermore demonstrates that gas-phase controlled systems are recommended where greater selectivity is required. Copyright © 2013 Elsevier Ltd. All rights reserved.

Theoretical investigation of the effects of the molar ratio and solvent on the formation of the pyrazole-nitroamine cocrystal explosive 3,4-dinitropyrazole (DNP)/2,4,6,8,10,12-hexanitrohexaazaisowurtzitane (CL-20).

PubMed

Zhu, Shuang-Fei; Zhang, Shu-Hai; Gou, Rui-Jun; Han, Gang; Wu, Chun-Lei; Ren, Fu-de

2017-11-24

The effects of the molar ratio, temperature, and solvent on the formation of the cocrystal explosive DNP/CL-20 were investigated using molecular dynamics (MD) simulation. The cocrystal structure was predicted through Monte Carlo (MC) simulation and using first-principles methods. The results showed that the DNP/CL-20 cocrystal might be more stable in the molar ratio 1:1 near to 318 K, and the most probable cocrystal crystallizes in the triclinic crystal system with the space group P[Formula: see text]. Cocrystallization was more likely to occur in methanol and ethanol at 308 K as a result of solvent effects. The optimized structure and the reduced density gradient (RDG) of the DNP/CL-20 complex confirmed that the main driving forces for cocrystallization were a series of hydrogen bonds and van der Waals forces. Analyses of the trigger bonds, the charges on the nitro groups, the electrostatic surface potential (ESP), and the free space per molecule in the cocrystal lattice were carried out to further explore their influences on the sensitivity of CL-20. The results indicated that the DNP/CL-20 complex tended to be more stable and insensitive than pure CL-20. Moreover, an investigation of the detonation performance of the DNP/CL-20 cocrystal indicated that it possesses high power. Graphical abstract DNP/CL-20 cocrystal models with different molar ratios were investigated at different temperatures using molecular dynamics (MD) simulation methods. Binding energies and mechanical properties were probed to determine the stability and performance of each cocrystal model. Solvated DNP/CL-20 models were established by adding solvent molecules to the cocrystal surface. The binding energies of the models in various solvents were calculated in order to identify the most suitable solvent and temperature for preparing the cocrystal explosive DNP/CL-20.

Direct coupling of microbore HPLC columns to MS systems

NASA Technical Reports Server (NTRS)

Mcnair, H. M.

1985-01-01

A detailed investigation using electron microscopy was conducted which examined the conditions of materials used in the construction of stable, high performance microbore liquid chromatography (LC) columns. Small details proved to be important. The effects of temperature on the elution of several homologous series used as probe compounds was examined in reverse phase systems. They showed that accessible temperature changes provide roughly half the increase in solvent strength that would be obtained going from a 100% aqueous to a 100% organic mobile phase, which is sufficient to warrant their use in many analyses requiring the use of gradients. Air circulation temperature control systems provide the easiest means of obtaining rapid, wide range changes in column temperature. However, slow heat transfer from the gas leads to thermal nonuniformity in the column and a decrease in resolution as the temperature program progresses.

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…

[Application of general retention time formula for gradient liquid chromatography in the studies of ladder-like gradient elution].

PubMed

Sun, Xiaoli; Hao, Weiqiang; Wang, Junde; Di, Bin; Chen, Qiang; Zhuang, Wei; Yu, Qiang; Zhang, Peipei

2013-08-01

By not explicitly specifying the type of solvent strength model, the features of ladder-like gradient elution were studied based on the general retention time formula that was derived in our previous work. For the case where the solute is eluted at like gradient, we derived the expression that connects the mobile phase composition (phiR), at which the solute is eluted from the column, with the gradient slope (B). It was shown that phiR will increase with the increase of B in this case. For the case where the solute is eluted at the last isocratic segment of the ladder-like gradient, it was proven that the retention time (tR) will correlate linearly with the reciprocal of the gradient slope (1/B) when the initial and final mobile phase compositions are set to be constant. In experiments, by taking biphenyl as the sample, the values of retention time in isocratic and gradient elution were measured on a C18 column by using a mixture of methanol and water as the mobile phase. The experimental values were found to be well consistent with the theoretical values that were calculated from the expressions. These expressions will be helpful to understand the features of the ladder-like gradient in practice.

Estimation of the nucleation kinetics for the anti-solvent crystallisation of paracetamol in methanol/water solutions

NASA Astrophysics Data System (ADS)

Ó'Ciardhá, Clifford T.; Frawley, Patrick J.; Mitchell, Niall A.

2011-08-01

In this work the primary nucleation kinetics have been estimated for the anti-solvent crystallisation of paracetamol in methanol-water solutions from metastable zone widths (MSZW) and induction times at 25 °C. Laser back-scattering via a focused beam reflectance Measurement (FBRM ®) is utilised to detect the onset of nucleation. The theoretical approach of Kubota was employed to estimate the nucleation kinetics, which accounts for the sensitivity of the nucleation detection technique. This approach is expanded in this work to analyse the induction time for an anti-solvent crystallisation process. Solvent composition is known to have a significant impact on the measured induction times and MSZW. The induction time in this paper was measured from 40% to 70% mass water and the MSZW is measured from 40% to 60% mass water. The primary focus of the paper was to gauge the extent of how solvent composition affects nucleation kinetics so that this effect may be incorporated into a population balance model. Furthermore, the effects of solvent composition on the estimated nucleation rates are investigated. The primary nucleation rates were found to decrease with dynamic solvent composition, with the extent of their reduction linked to the gradient of the solubility curve. Finally, both MSZW and induction time methods have been found to produce similar estimates for the nucleation parameters.

Permeability and electrical properties of planar lipid membranes from thylakoid lipids.

PubMed Central

Fuks, B; Homblé, F

1994-01-01

Electrical measurements were carried out on planar lipid membranes from thylakoid lipids. The specific capacitance of membranes formed from decane-containing monogalactosyldiacylglycerol (MGDG), which accounts for 57% of the total lipid content of thylakoids, showed that it adopted a bilayer structure. Solvent-free bilayers of MGDG were not formed, with very rare exceptions, indicating that decane is required to stabilize the planar conformation. However, this cone-shaped lipid produces bilayer structures in combination with other cylindrical thylakoid lipids even in the absence of organic solvent. We compared the properties of solvent-free and decane-containing bilayers from MGDG, soybean lecithin, and the quaternary mixture of lipids similar to that found in vivo. The conductance of decane-MGDG was 26 times higher than that of decane-lecithin. The flux through the decane-lecithin bilayer was found to be slightly dependent on pH, whereas the decane-MGDG membrane was not. The specific conductance of bilayers formed from the quaternary mixture of lipids was 5 to 10 times larger than lecithin (with alkane or not). Further experiments with bilayers made in the presence of a KCl gradient showed that decane-MGDG, decane-MGDG/DGDG/SQDG/PG, and solvent-free MGDG/DGDG/SQDG/PG were cation-selective. The permeability coefficient for potassium ranged from 4.9 to 8.3 x 10(-11) cm s-1. The permeability coefficient for protons in galactolipids, however, was determined to be about six orders of magnitude higher than the value for potassium ions. The HCl permeation mechanism through the lipid membranes was determined from diffusion potentials measured in HCl gradients. Our results suggest that HCl was not transported as neutral molecules. The data is discussed with regard to the function of galactolipids in the ion transport through thylakoid membranes. PMID:8061192

Study of mass transfer in supercritical carbon dioxide (SCCO2) using optical methods

NASA Astrophysics Data System (ADS)

Hu, M.; Benning, R.; Ertunç, Ö.; Delgado, A.; Nercissian, V.; Berger, M.

2017-12-01

The purpose of this work is to design and develop a type of experiment setup that would enable the direct observation of steady diffusion process in situ. Two different optical methods - shadowgraph and shearing interferometry - were used for the first time to visualise and quantitatively analyse the diffusion around a droplet of organic substance in supercritical carbon dioxide (SCCO2) as well as in its direct vicinity. We constructed and tested a cylindrical high-pressure chamber and an experiment system with a high speed camera. The solute/solvent combination of DL- α-tocopherol/SCCO2 was applied using shadowgraph. The diffusion coefficients at temperatures of 40o C, 50o C and 60o C and pressures between 75 bar and 90 bar were calculated based on the displacement of the droplet contour in the captured images. The shearing interferometry with a Wollaston-prism was then applied not only for the combination of DL- α-tocopherol/SCCO2, but also for other substances in SCCO2, for example for a type of rose oil and lubricant oil as well as for acetone, benzene, toluene and naphthalene. The changes of the refractive index gradient were directly measured and evaluated with the interferograms; afterwards changes of the density gradients and the diffusion coefficients were determined. We propose then a multivariate regression model to capture the relationship between the diffusion coefficient, the pressure and the temperature. To minimize the influence of gravity-driven convections in the solvent during diffusion, the experiments were also carried out under microgravity condition, i.e. in two parabolic flight campaigns.

Applications of MMPBSA to Membrane Proteins I: Efficient Numerical Solutions of Periodic Poisson-Boltzmann Equation

PubMed Central

Botello-Smith, Wesley M.; Luo, Ray

2016-01-01

Continuum solvent models have been widely used in biomolecular modeling applications. Recently much attention has been given to inclusion of implicit membrane into existing continuum Poisson-Boltzmann solvent models to extend their applications to membrane systems. Inclusion of an implicit membrane complicates numerical solutions of the underlining Poisson-Boltzmann equation due to the dielectric inhomogeneity on the boundary surfaces of a computation grid. This can be alleviated by the use of the periodic boundary condition, a common practice in electrostatic computations in particle simulations. The conjugate gradient and successive over-relaxation methods are relatively straightforward to be adapted to periodic calculations, but their convergence rates are quite low, limiting their applications to free energy simulations that require a large number of conformations to be processed. To accelerate convergence, the Incomplete Cholesky preconditioning and the geometric multi-grid methods have been extended to incorporate periodicity for biomolecular applications. Impressive convergence behaviors were found as in the previous applications of these numerical methods to tested biomolecules and MMPBSA calculations. PMID:26389966

Pressurized capillary electrochromatographic analysis of water-soluble vitamins by combining with on-line concentration technique.

PubMed

Jia, Li; Liu, Yaling; Du, Yanyan; Xing, Da

2007-06-22

A pressurized capillary electrochromatography (pCEC) system was developed for the separation of water-soluble vitamins, in which UV absorbance was used as the detection method and a monolithic silica-ODS column as the separation column. The parameters (type and content of organic solvent in the mobile phase, type and concentration of electrolyte, pH of the electrolyte buffer, applied voltage and flow rate) affecting the separation resolution were evaluated. The combination of two on-line concentration techniques, namely, solvent gradient zone sharpening effect and field-enhanced sample stacking, was utilized to improve detection sensitivity, which proved to be beneficial to enhance the detection sensitivity by enabling the injection of large volumes of samples. Coupling electrokinetic injection with the on-line concentration techniques was much more beneficial for the concentration of positively charged vitamins. Comparing with the conventional injection mode, the enhancement in the detection sensitivities of water-soluble vitamins using the on-line concentration technique is in the range of 3 to 35-fold. The developed pCEC method was applied to evaluate water-soluble vitamins in corns.

HPLC-UV Method for the Identification and Screening of Hydroquinone, Ethers of Hydroquinone and Corticosteroids Possibly Used as Skin-Whitening Agents in Illicit Cosmetic Products.

PubMed

Gimeno, Pascal; Maggio, Annie-Françoise; Bancilhon, Marjorie; Lassu, Nelly; Gornes, Hervé; Brenier, Charlotte; Lempereur, Laurent

2016-03-01

Corticosteroids, hydroquinone and its ethers are regulated in cosmetics by the Regulation 1223/2009. As corticosteroids are forbidden to be used in cosmetics and cannot be present as contaminants or impurities, an identification of one of these illicit compounds deliberately introduced in these types of cosmetics is enough for market survey control. In order to quickly identify skin-whitening agents present in illegal cosmetics, this article proposes an HPLC-UV method for the identification and screening of hydroquinone, 3 ethers of hydroquinone and 39 corticosteroids that may be found in skin-whitening products. Two elution gradients were developed to separate all compounds. The main solvent gradient (A) allows the separation of 39 compounds among the 43 compounds considered in 50 min. Limits of detection on skin-whitening cosmetics are given. For compounds not separated, a complementary gradient elution (B) using the same solvents is proposed. Between 2004 and 2009, a market survey on "skin-whitening cosmetic" was performed on 150 samples and highlights that more than half of the products tested do not comply with the Cosmetic Regulation 1223/2009 (amending the Council Directive 76/768/EEC). © The Author 2015. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

Combining selection valve and mixing chamber for nanoflow gradient generation: Toward developing a liquid chromatography cartridge coupled with mass spectrometer for protein and peptide analysis.

PubMed

Chen, Apeng; Lu, Joann J; Gu, Congying; Zhang, Min; Lynch, Kyle B; Liu, Shaorong

2015-08-05

Toward developing a micro HPLC cartridge, we have recently built a high-pressure electroosmotic pump (EOP). However, we do not recommend people to use this pump to deliver an organic solvent directly, because it often makes the pump rate unstable. We have experimented several approaches to address this issue, but none of them are satisfactory. Here, we develop an innovative approach to address this issue. We first create an abruption (a dead-volume) within a fluid conduit. We then utilize an EOP to withdraw, via a selection valve, a train of eluent solutions having decreasing eluting power into the fluid conduit. When these solutions are further aspirated through the dead-volume, these solutions are partially mixed, smoothening concentration transitions between two adjacent eluent solutions. As these solutions are pushed back, through the dead-volume again, a smooth gradient profile is formed. In this work, we characterize this scheme for gradient formation, and we incorporate this approach with a high-pressure EOP, a nanoliter injection valve, and a capillary column, yielding a micro HPLC system. We then couple this micro HPLC with an electrospray ionization - mass spectrometer for peptide and protein separations and identifications. Copyright © 2015 Elsevier B.V. All rights reserved.

Apparatus and method for removing solvent from carbon dioxide in resin recycling system

DOEpatents

Bohnert, George W [Harrisonville, MO; Hand, Thomas E [Lee's Summit, MO; DeLaurentiis, Gary M [Jamestown, CA

2009-01-06

A two-step resin recycling system and method solvent that produces essentially contaminant-free synthetic resin material. The system and method includes one or more solvent wash vessels to expose resin particles to a solvent, the solvent contacting the resin particles in the one or more solvent wash vessels to substantially remove contaminants on the resin particles. A separator is provided to separate the solvent from the resin particles after removal from the one or more solvent wash vessels. The resin particles are next exposed to carbon dioxide in a closed loop carbon dioxide system. The closed loop system includes a carbon dioxide vessel where the carbon dioxide is exposed to the resin, substantially removing any residual solvent remaining on the resin particles after separation. A separation vessel is also provided to separate the solvent from the solvent laden carbon dioxide. Both the carbon dioxide and the solvent are reused after separation in the separation vessel.

Tracking control of colloidal particles through non-homogeneous stationary flows

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

Híjar, Humberto, E-mail: humberto.hijar@lasallistas.org.mx

2013-12-21

We consider the problem of controlling the trajectory of a single colloidal particle in a fluid with steady non-homogeneous flow. We use a Langevin equation to describe the dynamics of this particle, where the friction term is assumed to be given by the Faxén's Theorem for the force on a sphere immersed in a stationary flow. We use this description to propose an explicit control force field to be applied on the particle such that it will follow asymptotically any given desired trajectory, starting from an arbitrary initial condition. We show that the dynamics of the controlled particle can bemore » mapped into a set of stochastic harmonic oscillators and that the velocity gradient of the solvent induces an asymmetric coupling between them. We study the particular case of a Brownian particle controlled through a plane Couette flow and show explicitly that the velocity gradient of the solvent renders the dynamics non-stationary and non-reversible in time. We quantify this effect in terms of the correlation functions for the position of the controlled particle, which turn out to exhibit contributions depending exclusively on the non-equilibrium character of the state of the solvent. In order to test the validity of our model, we perform simulations of the controlled particle moving in a simple shear flow, using a hybrid method combining molecular dynamics and multi-particle collision dynamics. We confirm numerically that the proposed guiding force allows for controlling the trajectory of the micro-sized particle by obligating it to follow diverse specific trajectories in fluids with homogeneous shear rates of different strengths. In addition, we find that the non-equilibrium correlation functions in simulations exhibit the same qualitative behavior predicted by the model, thus revealing the presence of the asymmetric non-equilibrium coupling mechanism induced by the velocity gradient.« less

Communication: Control of chemical reactions using electric field gradients.

PubMed

Deshmukh, Shivaraj D; Tsori, Yoav

2016-05-21

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

Continuous countercurrent membrane column for the separation of solute/solvent and solvent/solvent systems

DOEpatents

Nerad, Bruce A.; Krantz, William B.

1988-01-01

A reverse osmosis membrane process or hybrid membrane - complementary separator process for producing enriched product or waste streams from concentrated and dilute feed streams for both solvent/solvent and solute/solvent systems is described.

Solvent cleaning system and method for removing contaminants from solvent used in resin recycling

DOEpatents

Bohnert, George W [Harrisonville, MO; Hand, Thomas E [Lee's Summit, MO; DeLaurentiis, Gary M [Jamestown, CA

2009-01-06

A two step solvent and carbon dioxide based system that produces essentially contaminant-free synthetic resin material and which further includes a solvent cleaning system for periodically removing the contaminants from the solvent so that the solvent can be reused and the contaminants can be collected and safely discarded in an environmentally safe manner.

A novel 9 × 9 map-based solvent selection strategy for targeted counter-current chromatography isolation of natural products.

PubMed

Liang, Junling; Meng, Jie; Wu, Dingfang; Guo, Mengzhe; Wu, Shihua

2015-06-26

Counter-current chromatography (CCC) is an efficient liquid-liquid chromatography technique for separation and purification of complex mixtures like natural products extracts and synthetic chemicals. However, CCC is still a challenging process requiring some special technical knowledge especially in the selection of appropriated solvent systems. In this work, we introduced a new 9 × 9 map-based solvent selection strategy for CCC isolation of targets, which permit more than 60 hexane-ethyl acetate-methanol-water (HEMWat) solvent systems as the start candidates for the selection of solvent systems. Among these solvent systems, there are clear linear correlations between partition coefficient (K) and the system numbers. Thus, an appropriate CCC solvent system (i.e., sweet spot for K = 1) may be hit by measurement of k values of the target only in two random solvent systems. Besides this, surprisingly, we found that through two sweet spots, we could get a line ("Sweet line") where there are infinite sweet solvent systems being suitable for CCC separation. In these sweet solvent systems, the target has the same partition coefficient (K) but different solubilities. Thus, the better sweet solvent system with higher sample solubility can be obtained for high capacity CCC preparation. Furthermore, we found that there is a zone ("Sweet zone") where all solvent systems have their own sweet partition coefficients values for the target in range of 0.4 < K< 2.5 or extended range of 0.25 < K < 16. All results were validated by using 14 pure GUESSmix mimic natural products as standards and further confirmed by isolation of several targets including honokiol and magnolol from the extracts of Magnolia officinalis Rehd. Et Wils and tanshinone IIA from Salvia miltiorrhiza Bunge. In practice, it is much easier to get a suitable solvent system only by making a simple screening two to four HEMWat two-phase solvent systems to obtain the sweet line or sweet zone without special knowledge or comprehensive standards as references. This is an important advancement for solvent system selection and also will be very useful for isolation of current natural products including Traditional Chinese Medicines. Copyright © 2015 Elsevier B.V. All rights reserved.

NMR structure of biosynthetic engineered human insulin monomer B31(Lys)-B32(Arg) in water/acetonitrile solution. Comparison with the solution structure of native human insulin monomer.

PubMed

Bocian, Wojciech; Borowicz, Piotr; Mikołajczyk, Jerzy; Sitkowski, Jerzy; Tarnowska, Anna; Bednarek, Elzbieta; Głabski, Tadeusz; Tejchman-Małecka, Bozena; Bogiel, Monika; Kozerski, Lech

2008-10-01

A solution NMR-derived structure of a new long -acting, B31(Lys)-B32(Arg) (LysArg), engineered human insulin monomer, in H(2)O/CD(3)CN, 65/35 vol %, pH 3.6, is presented and compared with the available X-ray structure of a monomer that forms part of a hexamer (Smith, et al., Acta Crystallogr D 2003, 59, 474) and with NMR structure of human insulin in the same solvent (Bocian, et al., J Biomol NMR 2008, 40, 55-64). Detailed analysis using PFGSE NMR (Pulsed Field Gradient Spin Echo NMR) in dilution experiments and CSI analysis prove that the structure is monomeric in the concentration range 0.1-3 mM. The presence of long-range interstrand NOEs in a studied structure, relevant to the distances found in the crystal structure of the monomer, provides the evidence for conservation of the tertiary structure. Therefore the results suggest that this solvent system is a suitable medium for studying the native conformation of the protein, especially in situations (as found for insulins) in which extensive aggregation renders structure elucidations in water difficult or impossible. Starting from the structures calculated by the program CYANA, two different molecular dynamics (MD) simulated annealing refinement protocols were applied, either using the program AMBER in vacuum (AMBER_VC), or including a generalized Born solvent model (AMBER_GB). Here we present another independent evidence to the one presented recently by us (Bocian et al., J Biomol NMR 2008, 40, 55-64), that in water/acetonitrile solvent detailed structural and dynamic information can be obtained for important proteins that are naturally present as oligomers under native conditions. (c) 2008 Wiley Periodicals, Inc.

Development of a sensitive and rapid method for rifampicin impurity analysis using supercritical fluid chromatography.

PubMed

Li, Wei; Wang, Jun; Yan, Zheng-Yu

2015-10-10

A novel simple, fast and efficient supercritical fluid chromatography (SFC) method was developed and compared with RPLC method for the separation and determination of impurities in rifampicin. The separation was performed using a packed diol column and a mobile phase B (modifier) consisting of methanol with 0.1% ammonium formate (w/v) and 2% water (v/v). Overall satisfactory resolutions and peak shapes for rifampicin quinone (RQ), rifampicin (RF), rifamycin SV (RSV), rifampicin N-oxide (RNO) and 3-formylrifamycinSV (3-FR) were obtained by optimization of the chromatography system. With gradient elution of mobile phase, all of the impurities and the active were separated within 4 min. Taking full advantage of features of SFC (such as particular selectivity, non-sloping baseline in gradient elution, and without injection solvent effects), the method was successfully used for determination of impurities in rifampicin, with more impurity peaks detected, better resolution achieved and much less analysis time needed compared with conventional reversed-phase liquid chromatography (RPLC) methods. Copyright © 2015 Elsevier B.V. All rights reserved.

Negative Transference Numbers in Polymer Electrolytes

NASA Astrophysics Data System (ADS)

Pesko, Danielle; Timachova, Ksenia; Balsara, Nitash

Energy density and safety of conventional lithium-ion batteries is limited by the use of flammable organic liquids as a solvent for lithium salts. Polymer electrolytes have the potential to address both limitations. The poor performance of batteries with polymer electrolytes is generally attributed to low ionic conductivity. The purpose of our work is to show that another transport property, the cation transference number, t +, of polymer electrolytes is fundamentally different from that of conventional electrolytes. Our experimental approach, based on concentrated solution theory, indicates that t + of mixtures of poly(ethylene oxide) and LiTFSI salt are negative over most of the accessible concentration window. In contrast, approaches based on dilute solution theory suggest that t + in the same system is positive. In addition to presenting a new approach for determining t +, we also present data obtained from the steady-state current method, pulsed-field-gradient NMR, and the current-interrupt method. Discrepancies between different approaches are resolved. Our work implies that in the absence of concentration gradients, the net fluxes of both cations and anions are directed toward the positive electrode. Conventional liquid electrolytes do not suffer from this constraint.

Wrinkling of solidifying polymeric coatings

NASA Astrophysics Data System (ADS)

Basu, Soumendra Kumar

2005-07-01

In coatings, wrinkles are viewed as defects or as desired features for low gloss, and texture. In either case, discovering the origin of wrinkles and the conditions that lead to their formation is important. This research examines what wrinkling requires and proposes a mechanism to explain the observations. All curing wrinkling coatings contain multi-functional reactants. Upon curing, all develop a depth-wise gradient in solidification that result in a cross-linked elastic skin atop a viscous bottom layer. It is hypothesized that compressive stress develops in the skin when liquid below diffuses up into the skin. High enough compressive stress buckles the skin to produce wrinkles. The hypothesis is substantiated by experimental and theoretical evidences. Effects of various application and compositional parameters on wrinkle size in a liquid-applied acrylic coating and a powder-applied epoxy coating were examined. All three components, namely resin, cross-linker and catalyst blocked with at least equimolar volatile blocker, proved to be required for wrinkling. The wrinkling phenomenon was modeled with a theory that accounts for gradient generation, cross-linking reaction and skinning; predictions compared well with observations. Two-layer non-curing coatings that have a stiff elastic layer atop a complaint elastic bottom layer wrinkled when the top layer is compressed. The top layer was compressed by either moisture absorption or differential thermal expansion. Experimental observations compared well with predictions from a theory based on force balance in multilayer systems subjected to differential contraction or expansion. A model based on the Flory-Rehner free energy of a constrained cross-linked gel was constructed that predicts the compressive stress generated in a coating when it absorbs solvent. Linear stability analysis predicts that when a compressed elastic layer is attached atop a viscous layer, it is always unstable to buckles whose wavelength exceeds a critical value; more cross-linking and poor solvent produce higher wavelength, lower amplitude wrinkles. When a compressed elastic layer is attached atop an elastic layer and subjected to more than a critical compressive stress, it is unstable to intermediate wavelengths of buckling; better solvent, higher ratio of bottom-to-top layer thickness, and lower bottom layer modulus produce higher wavelength, higher amplitude wrinkles.

Qualitative and quantitative evaluation of solvent systems for countercurrent separation.

PubMed

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

2015-01-16

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

Comparison of retention models for polymers 1. Poly(ethylene glycol)s.

PubMed

Bashir, Mubasher A; Radke, Wolfgang

2006-10-27

The suitability of three different retention models to predict the retention times of poly(ethylene glycol)s (PEGs) in gradient and isocratic chromatography was investigated. The models investigated were the linear (LSSM) and the quadratic solvent strength model (QSSM). In addition, a model describing the retention behaviour of polymers was extended to account for gradient elution (PM). It was found that all models are suited to properly predict gradient retention volumes provided the extraction of the analyte specific parameters is performed from gradient experiments as well. The LSSM and QSSM on principle cannot describe retention behaviour under critical or SEC conditions. Since the PM is designed to cover all three modes of polymer chromatography, it is therefore superior to the other models. However, the determination of the analyte specific parameters, which are needed to calibrate the retention behaviour, strongly depend on the suitable selection of initial experiments. A useful strategy for a purposeful selection of these calibration experiments is proposed.

First hyperpolarizability of isomers of pyridinium N-phenoxide betaine dye in solution using the ASEC-FEG method

NASA Astrophysics Data System (ADS)

Torres, E. M.; Georg, H. C.; Fonseca, T. L.; Castro, M. A.

2018-05-01

The linear and nonlinear properties of isomeric forms of pyridinium-N-phenoxide betaine dye were investigated in protic and aprotic solvents using atomistic simulations. We employed the sequential Quantum Mechanics/Molecular Mechanics (S-QM/MM) and the free energy gradient (FEG) methods to optimize the geometry of each isomer in chloroform, acetonitrile, methanol and water. The results show a complex dependence of the first hyperpolarizability with respect to the solvent nature and isomeric form, with a marked effect of conformational changes for para-betaine. Large contrasts of the first hyperpolarizability show a clear distinction between isomeric forms in solution that could be experimentally detected.

A rapid screening procedure for drugs and poisons in gastric contents by direct injection-HPLC analysis.

PubMed

Politi, Lucia; Groppi, Angelo; Polettini, Aldo; Montagna, Maria

2004-05-10

A high performance liquid chromatographic method for toxicological drug screening of gastric content has been developed. The samples were diluted (1:3-1:30) in 0.01 N hydrochloric acid and injected into a reverse phase column for separation by gradient elution. Mobile phase consisted of solvent A (acetonitrile/water 90:10, 0.01 M sodium dodecylsulphate, 0.5% v/v glacial acetic acid) and solvent B (water/acetonitrile 90:10, 0.01 M sodium dodecylsulphate, 0.5% v/v glacial acetic acid); the gradient was programmed from 20 to 80% A in 30 min. The flow was kept constant at 1.5 ml/min. Two home-made internal standards, butyrylsalicylic acid and diacetyltubocurarine with retention times of 5.6 and 21.4 min, respectively, were used. Drugs are identified by matching their relative retention times and UV spectra (200-400 nm) with those contained in a home made library of more than 340 reference compounds (9 analgesics, 22 antidepressants, 30 antihistamines, 14 antihypertensives, 21 antirheumatics, 15 beta-blockers, 9 bronchodilators, 10 Ca antagonists, 14 diuretics, 26 neuroleptics, 25 tranquilizers, and other significant xenobiotic compounds). The fluorometric (FLD) emission spectrum (280-700 nm; excitation wavelength, 230 nm) was used as a further identification. At 50mg/l analyte concentrations, the injection of gastric content after dilution (1:3) produced S/N ratios in the range 8-140. The method is simple, rapid, rather inexpensive and proved to be a useful means of investigation if used in combination with GC-MS screening in blood. On the other hand, the system suffers from a relatively limited sensitivity for compounds with a low UV absorption and from interferences due to the presence in the matrix of some highly UV- and FL-responsive compounds (e.g. tryptophan).

Many-body dynamics of chemically propelled nanomotors

NASA Astrophysics Data System (ADS)

Colberg, Peter H.; Kapral, Raymond

2017-08-01

The collective behavior of chemically propelled sphere-dimer motors made from linked catalytic and noncatalytic spheres in a quasi-two-dimensional confined geometry is studied using a coarse-grained microscopic dynamical model. Chemical reactions at the catalytic spheres that convert fuel to product generate forces that couple to solvent degrees of freedom as a consequence of momentum conservation in the microscopic dynamics. The collective behavior of the many-body system is influenced by direct intermolecular interactions among the motors, chemotactic effects due to chemical gradients, hydrodynamic coupling, and thermal noise. Segregation into high and low density phases and globally homogeneous states with strong fluctuations are investigated as functions of the motor characteristics. Factors contributing to this behavior are discussed in the context of active Brownian models.

Pretreatment of Lignocellulosic Biomass with Ionic Liquids and Ionic Liquid-Based Solvent Systems.

PubMed

Hou, Qidong; Ju, Meiting; Li, Weizun; Liu, Le; Chen, Yu; Yang, Qian

2017-03-20

Pretreatment is very important for the efficient production of value-added products from lignocellulosic biomass. However, traditional pretreatment methods have several disadvantages, including low efficiency and high pollution. This article gives an overview on the applications of ionic liquids (ILs) and IL-based solvent systems in the pretreatment of lignocellulosic biomass. It is divided into three parts: the first deals with the dissolution of biomass in ILs and IL-based solvent systems; the second focuses on the fractionation of biomass using ILs and IL-based solvent systems as solvents; the third emphasizes the enzymatic saccharification of biomass after pretreatment with ILs and IL-based solvent systems.

Ultramicroelectrode Sensors and Detectors. Considerations of the Stability, Sensitivity, Reproducibility, and Mechanism of Ion Transport in Gas Phase Chromatography and in High Performance Liquid Phase Chromatography

DTIC Science & Technology

1988-07-15

solvents were used. For high performance liquid chromatographic studies, the DNA bases thymine, adenine, cytocine, uracil, and guanine (Aldrich...this experiment. The DNA bases guanine, adenine, cytocine, uracil, and thymine were detected for a gradient elution of a mixture of the bases in a

New approaches with two cyano columns to the separation of acetaminophen, phenylephrine, chlorpheniramine and related compounds.

PubMed

Olmo, B; García, A; Marín, A; Barbas, C

2005-03-25

The development of new pharmaceutical forms with classical active compounds generates new analytical problems. That is the case of sugar-free sachets of cough-cold products containing acetaminophen, phenylephrine hydrochloride and chlorpheniramine maleate. Two cyanopropyl stationary phases have been employed to tackle the problem. The Discovery cyanopropyl (SUPELCO) column permitted the separation of the three actives, maleate and excipients (mainly saccharine and orange flavour) with a constant proportion of aqueous/ organic solvent (95:5, v/v) and a pH gradient from 7.5 to 2. The run lasted 14 min. This technique avoids many problems related to baseline shifts with classical organic solvent gradients and opens great possibilities to modify selectivity not generally used in reversed phase HPLC. On the other hand, the Agilent Zorbax SB-CN column with a different retention profile permitted us to separate not only the three actives and the excipients but also the three known related compounds: 4-aminophenol, 4-chloracetanilide and 4-nitrophenol in an isocratic method with a run time under 30 min. This method was validated following ICH guidelines and validation parameters showed that it could be employed as stability-indicating method for this pharmaceutical form.

Three-dimensional desirability spaces for quality-by-design-based HPLC development.

PubMed

Mokhtar, Hatem I; Abdel-Salam, Randa A; Hadad, Ghada M

2015-04-01

In this study, three-dimensional desirability spaces were introduced as a graphical representation method of design space. This was illustrated in the context of application of quality-by-design concepts on development of a stability indicating gradient reversed-phase high-performance liquid chromatography method for the determination of vinpocetine and α-tocopheryl acetate in a capsule dosage form. A mechanistic retention model to optimize gradient time, initial organic solvent concentration and ternary solvent ratio was constructed for each compound from six experimental runs. Then, desirability function of each optimized criterion and subsequently the global desirability function were calculated throughout the knowledge space. The three-dimensional desirability spaces were plotted as zones exceeding a threshold value of desirability index in space defined by the three optimized method parameters. Probabilistic mapping of desirability index aided selection of design space within the potential desirability subspaces. Three-dimensional desirability spaces offered better visualization and potential design spaces for the method as a function of three method parameters with ability to assign priorities to this critical quality as compared with the corresponding resolution spaces. © The Author 2014. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

A new finite element and finite difference hybrid method for computing electrostatics of ionic solvated biomolecule

NASA Astrophysics Data System (ADS)

Ying, Jinyong; Xie, Dexuan

2015-10-01

The Poisson-Boltzmann equation (PBE) is one widely-used implicit solvent continuum model for calculating electrostatics of ionic solvated biomolecule. In this paper, a new finite element and finite difference hybrid method is presented to solve PBE efficiently based on a special seven-overlapped box partition with one central box containing the solute region and surrounded by six neighboring boxes. In particular, an efficient finite element solver is applied to the central box while a fast preconditioned conjugate gradient method using a multigrid V-cycle preconditioning is constructed for solving a system of finite difference equations defined on a uniform mesh of each neighboring box. Moreover, the PBE domain, the box partition, and an interface fitted tetrahedral mesh of the central box can be generated adaptively for a given PQR file of a biomolecule. This new hybrid PBE solver is programmed in C, Fortran, and Python as a software tool for predicting electrostatics of a biomolecule in a symmetric 1:1 ionic solvent. Numerical results on two test models with analytical solutions and 12 proteins validate this new software tool, and demonstrate its high performance in terms of CPU time and memory usage.

Simulation of electric double-layer capacitors: evaluation of constant potential method

NASA Astrophysics Data System (ADS)

Wang, Zhenxing; Laird, Brian; Yang, Yang; Olmsted, David; Asta, Mark

2014-03-01

Atomistic simulations can play an important role in understanding electric double-layer capacitors (EDLCs) at a molecular level. In such simulations, typically the electrode surface is modeled using fixed surface charges, which ignores the charge fluctuation induced by local fluctuations in the electrolyte solution. In this work we evaluate an explicit treatment of charges, namely constant potential method (CPM)[1], in which the electrode charges are dynamically updated to maintain constant electrode potential. We employ a model system with a graphite electrode and a LiClO4/acetonitrile electrolyte, examined as a function of electrode potential differences. Using various molecular and macroscopic properties as metrics, we compare CPM simulations on this system to results using fixed surface charges. Specifically, results for predicted capacity, electric potential gradient and solvent density profile are identical between the two methods; However, ion density profiles and solvation structure yield significantly different results.

Directional transport of colloids inside a bath of self-propelling walkers.

PubMed

Merlitz, Holger; Wu, Chenxu; Sommer, Jens-Uwe

2017-05-24

We present a setup in which passive colloids inside a solvent are moved to the boundaries of the container. The directional transport is facilitated by self-propelling microparticles ("walkers") with an activity gradient, which reduces their propulsion in the vicinity of bounding walls. An attractive interaction leads to the adsorption of walkers onto the colloid-surfaces in regions of low walker activity. It is shown that the activity gradient generates a free energy gradient which in turn acts as a driving force on the passive colloids. We carry out molecular dynamics simulations and present approaches to a theoretical description of the involved processes. Although the simulation data are not reproduced on a fully quantitative level, their qualitative features are covered by the model. The effect described here may be applied to facilitate a directional transport of drugs or to eliminate pollutants.

Emergent Chemical Behavior in Variable-Volume Protocells

PubMed Central

Shirt-Ediss, Ben; Solé, Ricard V.; Ruiz-Mirazo, Kepa

2015-01-01

Artificial protocellular compartments and lipid vesicles have been used as model systems to understand the origins and requirements for early cells, as well as to design encapsulated reactors for biotechnology. One prominent feature of vesicles is the semi-permeable nature of their membranes, able to support passive diffusion of individual solute species into/out of the compartment, in addition to an osmotic water flow in the opposite direction to the net solute concentration gradient. Crucially, this water flow affects the internal aqueous volume of the vesicle in response to osmotic imbalances, in particular those created by ongoing reactions within the system. In this theoretical study, we pay attention to this often overlooked aspect and show, via the use of a simple semi-spatial vesicle reactor model, that a changing solvent volume introduces interesting non-linearities into an encapsulated chemistry. Focusing on bistability, we demonstrate how a changing volume compartment can degenerate existing bistable reactions, but also promote emergent bistability from very simple reactions, which are not bistable in bulk conditions. One particularly remarkable effect is that two or more chemically-independent reactions, with mutually exclusive reaction kinetics, are able to couple their dynamics through the variation of solvent volume inside the vesicle. Our results suggest that other chemical innovations should be expected when more realistic and active properties of protocellular compartments are taken into account. PMID:25590570

A Technique for Thermal Desorption Analyses Suitable for Thermally-Labile, Volatile Compounds.

PubMed

Alborn, Hans T

2018-02-01

Many plant and insect interactions are governed by odors released by the plants or insects and there exists a continual need for new or improved methods to collect and identify these odors. Our group has for some time studied below-ground, plant-produced volatile signals affecting nematode and insect behavior. The research requires repeated sampling of volatiles of intact plant/soil systems in the laboratory as well as the field with the help of probes to minimize unwanted effects on the systems we are studying. After evaluating solid adsorbent filters with solvent extraction or solid phase micro extraction fiber sample collection, we found dynamic sampling of small air volumes on Tenax TA filters followed by thermal desorption sample introduction to be the most suitable analytical technique for our applications. Here we present the development and evaluation of a low-cost and relatively simple thermal desorption technique where a cold trap cooled with liquid carbon dioxide is added as an integral part of a splitless injector. Temperature gradient-based focusing and low thermal mass minimizes aerosol formation and eliminates the need for flash heating, resulting in low sample degradation comparable to solvent-based on-column injections. Additionally, since the presence of the cold trap does not affect normal splitless injections, on-the-fly switching between splitless and thermal desorption modes can be used for external standard quantification.

A straightforward method for measuring the range of apparent density of microplastics.

PubMed

Li, Lingyun; Li, Mengmeng; Deng, Hua; Cai, Li; Cai, Huiwen; Yan, Beizhan; Hu, Jun; Shi, Huahong

2018-10-15

Density of microplastics has been regarded as the primary property that affect the distribution and bioavailability of microplastics in the water column. For measuring the density of microplastis, we developed a simple and rapid method based on density gradient solutions. In this study, we tested four solvents to make the density gradient solutions, i.e., ethanol (0.8 g/cm 3 ), ultrapure water (1.0 g/cm 3 ), saturated NaI (1.8 g/cm 3 ) and ZnCl 2 (1.8 g/cm 3 ). Density of microplastics was measured via observing the float or sink status in the density gradient solutions. We found that density gradient solutions made from ZnCl 2 had a larger uncertainty in measuring density than that from NaI, most likely due to a higher surface tension of ZnCl 2 solution. Solutions made from ethanol, ultrapure water, and NaI showed consistent density results with listed densities of commercial products, indicating that these density gradient solutions were suitable for measuring microplastics with a density range of 0.8-1.8 g/cm 3 . Copyright © 2018 Elsevier B.V. All rights reserved.

Method for efficient recovery of high-purity polycarbonates from electronic waste.

PubMed

Weeden, George S; Soepriatna, Nicholas H; Wang, Nien-Hwa Linda

2015-02-17

More than one million tons of polycarbonates from waste electrical and electronic equipment are consigned to landfills at an increasing rate of 3-5% per year. Recycling the polymer waste should have a major environmental impact. Pure solvents cannot be used to selectively extract polycarbonates from mixtures of polymers with similar properties. In this study, selective mixed solvents are found using guidelines from Hansen solubility parameters, gradient polymer elution chromatography, and solubility tests. A room-temperature sequential extraction process using two mixed solvents is developed to recover polycarbonates with high yield (>95%) and a similar purity and molecular weight distribution as virgin polycarbonates. The estimated cost of recovery is less than 30% of the cost of producing virgin polycarbonates from petroleum. This method would potentially reduce raw materials from petroleum, use 84% less energy, reduce emission by 1-6 tons of CO2 per ton of polycarbonates, and reduce polymer accumulation in landfills and associated environmental hazards.

System for removing contaminants from plastic resin

DOEpatents

Bohnert, George W.; Hand, Thomas E.; DeLaurentiis, Gary M.

2010-11-23

A resin recycling system that produces essentially contaminant-free synthetic resin material in an environmentally safe and economical manner. The system includes receiving the resin in container form. A grinder grinds the containers into resin particles. The particles are exposed to a solvent in one or more solvent wash vessels, the solvent contacting the resin particles and substantially removing contaminants on the resin particles. A separator is used to separate the resin particles and the solvent. The resin particles are then placed in solvent removing element where they are exposed to a solvent removing agent which removes any residual solvent remaining on the resin particles after separation.

Extraction and identification of flavonoids from parsley extracts by HPLC analysis

NASA Astrophysics Data System (ADS)

Stan, M.; Soran, M. L.; Varodi, C.; Lung, I.

2012-02-01

Flavonoids are phenolic compounds isolated from a wide variety of plants, and are valuable for their multiple properties, including antioxidant and antimicrobial activities. In the present work, parsley (Petroselinum crispum L.) extracts were obtained by three different extraction techniques: maceration, ultrasonic-assisted and microwave-assisted solvent extractions. The extractions were performed with ethanol-water mixtures in various ratios. From these extracts, flavonoids like the flavones apigenin and luteolin, and the flavonols quercetin and kaempferol were identified using an HPLC Shimadzu apparatus equipped with PDA and MS detectors. The separation method involved a gradient step. The mobile phase consisted of two solvents: acetonitrile and distilled water with 0.1% formic acid. The separation was performed on a RP-C18 column.

Solvent effects on infrared spectra of progesterone in CHCl 3/ cyclo-C 6H 12 binary solvent systems

NASA Astrophysics Data System (ADS)

Liu, Qing; Wang, Xiao-yan; Zhang, Hui

2007-01-01

The infrared spectroscopy studies of the C 3 and C 20 carbonyl stretching vibrations ( υ(C dbnd O)) of progesterone in CHCl 3/ cyclo-C 6H 12 binary solvent systems were undertaken to investigate the solute-solvent interactions. With the mole fraction of CHC1 3 in the binary solvent mixtures increase, three types of C 3 and C 20 carbonyl stretching vibration band of progesterone are observed, respectively. The assignments of υ(C dbnd O) of progesterone are discussed in detail. In the CHCl 3-rich binary solvent systems or pure CHCl 3 solvent, two kinds of solute-solvent hydrogen bonding interactions coexist for C 20 C dbnd O. Comparisons are drawn for the solvent sensitivities of υ(C dbnd O) for acetophenone and 5α-androstan-3,17-dione, respectively.

Controlling Actinide Hydration in Mixed Solvent Systems: Towards Tunable Solvent Systems to Close the Fuel Cycle

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

Clark, Sue B.

2016-10-31

The goal of this project has been to define the extent of hydration the f-elements and other cations in mixed solvent electrolyte systems. Methanol-water and other mixed solvent systems have been studied, where the solvent dielectric constant was varied systematically. Thermodynamic and spectroscopic studies provide details concerning the energetics of complexation and other reactions of these cations. This information has also been used to advance new understanding of the behavior of these cations in a variety of systems, ranging from environmental studies, chromatographic approaches, and ionization processes for mass spectrometry.

Microscale solution manipulation using photopolymerized hydrogel membranes and induced charge electroosmosis micropumps

NASA Astrophysics Data System (ADS)

Paustian, Joel Scott

Microfluidic technology is playing an ever-expanding role in advanced chemical and biological devices, with diverse applications including medical diagnostics, high throughput research tools, chemical or biological detection, separations, and controlled particle fabrication. Even so, local (microscale) modification of solution properties within microchannels, such as pressure, solute concentration, and voltage remains a challenge, and improved spatiotemporal control would greatly enhance the capabilities of microfluidics. This thesis demonstrates and characterizes two microfluidic tools to enhance local solution control. I first describe a microfluidic pump that uses an electrokinetic effect, Induced-Charge Electroosmosis (ICEO), to generate pressure on-chip. In ICEO, steady flows are driven by AC fields along metal-electrolyte interfaces. I design and microfabricate a pump that exploits this effect to generate on-chip pressures. The ICEO pump is used to drive flow along a microchannel, and the pressure is measured as a function of voltage, frequency, and electrolyte composition. This is the first demonstration of chip-scale flows driven by ICEO, which opens the possibility for ICEO pumping in self-contained microfluidic devices. Next, I demonstrate a method to create thin local membranes between microchannels, which enables local diffusive delivery of solute. These ``Hydrogel Membrane Microwindows'' are made by photopolymerizing a hydrogel which serves as a local ``window'' for solute diffusion and electromigration between channels, but remains a barrier to flow. I demonstrate three novel experimental capabilities enabled by the hydrogel membranes: local concentration gradients, local electric currents, and rapid diffusive composition changes. I conclude by applying the hydrogel membranes to study solvophoresis, the migration of particles in solvent gradients. Solvent gradients are present in many chemical processes, but migration of particles within these gradients is not well understood. An improved understanding would allow solvophoresis to be engineered (e.g. for coatings and thin film deposition) or reduced (e.g. in fouling processes during reactions and separations). Toward this end, I perform velocity measurements of colloidal particles at various ethanol-water concentrations and gradient strengths. The velocity was found to depend on the mole fraction via the equation u = DSP▿ln X, where u is the velocity, DSP is the mobility, and X is the ethanol mole fraction.

Large scale micro-photometry for high resolution pH-characterization during electro-osmotic pumping and modular micro-swimming

NASA Astrophysics Data System (ADS)

Niu, Ran; Khodorov, Stanislav; Weber, Julian; Reinmüller, Alexander; Palberg, Thomas

2017-11-01

Micro-fluidic pumps as well as artificial micro-swimmers are conveniently realized exploiting phoretic solvent flows based on local gradients of temperature, electrolyte concentration or pH. We here present a facile micro-photometric method for monitoring pH gradients and demonstrate its performance and scope on different experimental situations including an electro-osmotic pump and modular micro-swimmers assembled from ion exchange resin beads and polystyrene colloids. In combination with the present microscope and DSLR camera our method offers a 2 μm spatial resolution at video frame rate over a field of view of 3920 × 2602 μm2. Under optimal conditions we achieve a pH-resolution of 0.05 with about equal contributions from statistical and systematical uncertainties. Our quantitative micro-photometric characterization of pH gradients which develop in time and reach out several mm is anticipated to provide valuable input for reliable modeling and simulations of a large variety of complex flow situations involving pH-gradients including artificial micro-swimmers, microfluidic pumping or even electro-convection.

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

PubMed

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

2000-10-27

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

Solute-Solvent Charge-Transfer Excitations and Optical Absorption of Hydrated Hydroxide from Time-Dependent Density-Functional Theory.

PubMed

Opalka, Daniel; Sprik, Michiel

2014-06-10

The electronic structure of simple hydrated ions represents one of the most challenging problems in electronic-structure theory. Spectroscopic experiments identified the lowest excited state of the solvated hydroxide as a charge-transfer-to-solvent (CTTS) state. In the present work we report computations of the absorption spectrum of the solvated hydroxide ion, treating both solvent and solute strictly at the same level of theory. The average absorption spectrum up to 25 eV has been computed for samples taken from periodic ab initio molecular dynamics simulations. The experimentally observed CTTS state near the onset of the absorption threshold has been analyzed at the generalized-gradient approximation (GGA) and with a hybrid density-functional. Based on results for the lowest excitation energies computed with the HSE hybrid functional and a Davidson diagonalization scheme, the CTTS transition has been found 0.6 eV below the first absorption band of liquid water. The transfer of an electron to the solvent can be assigned to an excitation from the solute 2pπ orbitals, which are subject to a small energetic splitting due to the asymmetric solvent environment, to the significantly delocalized lowest unoccupied orbital of the solvent. The distribution of the centers of the excited state shows that CTTS along the OH(-) axis of the hydroxide ion is avoided. Furthermore, our simulations indicate that the systematic error arising in the calculated spectrum at the GGA originates from a poor description of the valence band energies in the solution.

Aminosilicone solvent recovery methods and systems

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

Spiry, Irina Pavlovna; Perry, Robert James; Wood, Benjamin Rue

The present invention is directed to aminosilicone solvent recovery methods and systems. The methods and systems disclosed herein may be used to recover aminosilicone solvent from a carbon dioxide containing vapor stream, for example, a vapor stream that leaves an aminosilicone solvent desorber apparatus. The methods and systems of the invention utilize a first condensation process at a temperature from about 80.degree. C. to about 150.degree. C. and a second condensation process at a temperature from about 5.degree. C. to about 75.degree. C. The first condensation process yields recovered aminosilicone solvent. The second condensation process yields water.

Efficacy of two rotary retreatment systems in removing Gutta-percha and sealer during endodontic retreatment with or without solvent: A comparative in vitro study.

PubMed

Bhagavaldas, Moushmi Chalakkarayil; Diwan, Abhinav; Kusumvalli, S; Pasha, Shiraz; Devale, Madhuri; Chava, Deepak Chowdary

2017-01-01

The aim of this in vitro study was to compare the efficacy of two retreatment rotary systems in the removal of Gutta-percha (GP) and sealer from the root canal walls with or without solvent. Forty-eight extracted human mandibular first premolars were prepared and obturated with GP and AH Plus sealer. Samples were then randomly divided into four groups. Group I was retreated with MtwoR rotary system without solvent, Group II was retreated with MtwoR rotary system with Endosolv R as the solvent, Group III with D-RaCe rotary system without solvent, and Group IV with D-RaCe rotary system and Endosolv R solvent. The cleanliness of canal walls was determined by stereomicroscope (×20) and AutoCAD software. Kruskal-Wallis test and Mann-Whitney U-test were used to compare the data. Results showed that none of the retreatment systems used in this study was able to completely remove the root canal filling material. D-RaCe with or without solvent showed significantly ( P > 0.05) less filling material at all levels compared to MtwoR with/without solvent. Within the limitation of the current study, D-RaCe rotary retreatment system is more effective in removing filling material from root canal walls when compared to MtwoR rotary retreatment system.

Activity and conformation of lysozyme in molecular solvents, protic ionic liquids (PILs) and salt-water systems.

PubMed

Wijaya, Emmy C; Separovic, Frances; Drummond, Calum J; Greaves, Tamar L

2016-09-21

Improving protein stabilisation is important for the further development of many applications in the pharmaceutical, specialty chemical, consumer product and agricultural sectors. However, protein stabilization is highly dependent on the solvent environment and, hence, it is very complex to tailor protein-solvent combinations for stable protein maintenance. Understanding solvent features that govern protein stabilization will enable selection or design of suitable media with favourable solution environments to retain protein native conformation. In this work the structural conformation and activity of lysozyme in 29 solvent systems were investigated to determine the role of various solvent features on the stability of the enzyme. The solvent systems consisted of 19 low molecular weight polar solvents and 4 protic ionic liquids (PILs), both at different water content levels, and 6 aqueous salt solutions. Small angle X-ray scattering, Fourier transform infrared spectroscopy and UV-vis spectroscopy were used to investigate the tertiary and secondary structure of lysozyme along with the corresponding activity in various solvation systems. At low non-aqueous solvent concentrations (high water content), the presence of solvents and salts generally maintained lysozyme in its native structure and enhanced its activity. Due to the presence of a net surface charge on lysozyme, electrostatic interactions in PIL-water systems and salt solutions enhanced lysozyme activity more than the specific hydrogen-bond interactions present in non-ionic molecular solvents. At higher solvent concentrations (lower water content), solvents with a propensity to exhibit the solvophobic effect, analogous to the hydrophobic effect in water, retained lysozyme native conformation and activity. This solvophobic effect was observed particularly for solvents which contained hydroxyl moieties. Preferential solvophobic effects along with bulky chemical structures were postulated to result in less competition with water at the specific hydration layer around the protein, thus reducing protein-solvent interactions and retaining lysozyme's native conformation. The structure-property links established in this study are considered to be applicable to other proteins.

FTIR Imaging Coupled with Multivariate Analysis for Study of Initial Diffusion of Different Solvents in Cellulose Acetate Butyrate Films

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

Lindblad, M.S.; Keyes, B.; Gedvilas, L.

Fourier transform infrared (FTIR) spectroscopic imaging was used to study the initial diffusion of different solvents in cellulose acetate butyrate (CAB) films containing different amounts of acetyl and butyryl substituents. Different solvents and solvent/non-solvent mixtures were also studied. The FTIR imaging system allowed acquisition of sequential images of the CAB films as solvent penetration proceeded without disturbing the system. The interface between the non-swollen polymer and the initial swelling front could be identified using multivariate data analysis tools. For a series of ketone solvents the initial diffusion coefficients and diffusion rates could be quantified and were found to be relatedmore » to the polar and hydrogen interaction parameters in the Hansen solubility parameters of the solvents. For the solvent/non-solvent system the initial diffusion rate decreased less than linearly with the weight-percent of non-solvent present in the solution, which probably was due to the swelling characteristic of the non-solvent. For a given solvent, increasing the butyryl content of the CAB increased the initial diffusion rate. Increasing the butyryl content from 17 wt.% butyryl to 37 wt.% butyryl produced a considerably larger increase in initial diffusion rate compared to an increase in butyryl content from 37 wt.% to 50 wt.% butyryl.« less

Computational solvent system screening for the separation of tocopherols with centrifugal partition chromatography using deep eutectic solvent-based biphasic systems.

PubMed

Bezold, Franziska; Weinberger, Maria E; Minceva, Mirjana

2017-03-31

Tocopherols are a class of molecules with vitamin E activity. Among those, α-tocopherol is the most important vitamin E source in the human diet. The purification of tocopherols involving biphasic liquid systems can be challenging since these vitamins are poorly soluble in water. Deep eutectic solvents (DES) can be used to form water-free biphasic systems and have already proven applicable for centrifugal partition chromatography separations. In this work, a computational solvent system screening was performed using the predictive thermodynamic model COSMO-RS. Liquid-liquid equilibria of solvent systems composed of alkanes, alcohols and DES, as well as partition coefficients of α-tocopherol, β-tocopherol, γ-tocopherol, and σ-tocopherol in these biphasic solvent systems were calculated. From the results the best suited biphasic solvent system, namely heptane/ethanol/choline chloride-1,4-butanediol, was chosen and a batch injection of a tocopherol mixture, mainly consisting of α- and γ-tocopherol, was performed using a centrifugal partition chromatography set up (SCPE 250-BIO). A separation factor of 1.74 was achieved for α- and γ-tocopherol. Copyright © 2017 Elsevier B.V. All rights reserved.

Continuous gradient scaffolds for rapid screening of cell-material interactions and interfacial tissue regeneration

PubMed Central

Bailey, Brennan M.; Nail, Lindsay N.; Grunlan, Melissa A.

2013-01-01

In tissue engineering, the physical and chemical properties of the scaffold mediates cell behavior including regeneration. Thus, a strategy that permits rapid screening of cell-scaffold interactions is critical. Herein, we have prepared eight “hybrid” hydrogel scaffolds in the form of continuous gradients such that a single scaffold contains spatially varied properties. These scaffolds are based on combining an inorganic macromer [methacrylated star polydimethylsiloxane, PDMSstar-MA] and organic macromer [poly(ethylene glycol)diacrylate, PEG-DA] as well both aqueous and organic fabrication solvents. Having previously demonstrated its bioactivity and osteoinductivity, PDMSstar-MA is a particularly powerful component to incorporate into instructive gradient scaffolds based on PEG-DA. The following parameters were varied to produce the different gradients or gradual transitions in: (1) the wt% ratio of PDMSstar-MA to PEG-DA macromers, (2) the total wt% macromer concentration, (3) the number average molecular weight (Mn) of PEG-DA and (4) the Mn of PDMSstar-MA. Upon dividing each scaffold into four “zones” perpendicular to the gradient, we were able to demonstrate the spatial variation in morphology, bioactivity, swelling and modulus. Among these gradient scaffolds are those in which swelling and modulus are conveniently decoupled. In addition to rapid screening of cell-material interactions, these scaffolds are well-suited for regeneration of interfacial tissues (e.g. osteochondral tissues) that transition from one tissue type to another. PMID:23707502

Physicochemical characterization and failure analysis of military coating systems

NASA Astrophysics Data System (ADS)

Keene, Lionel Thomas

Modern military coating systems, as fielded by all branches of the U.S. military, generally consist of a diverse array of organic and inorganic components that can complicate their physicochemical analysis. These coating systems consist of VOC-solvent/waterborne automotive grade polyurethane matrix containing a variety of inorganic pigments and flattening agents. The research presented here was designed to overcome the practical difficulties regarding the study of such systems through the combined application of several cross-disciplinary techniques, including vibrational spectroscopy, electron microscopy, microtomy, ultra-fast laser ablation and optical interferometry. The goal of this research has been to determine the degree and spatial progression of weathering-induced alteration of military coating systems as a whole, as well as to determine the failure modes involved, and characterizing the impact of these failures on the physical barrier performance of the coatings. Transmission-mode Fourier Transform Infrared (FTIR) spectroscopy has been applied to cross-sections of both baseline and artificially weathered samples to elucidate weathering-induced spatial gradients to the baseline chemistry of the coatings. A large discrepancy in physical durability (as indicated by the spatial progression of these gradients) has been found between older and newer generation coatings. Data will be shown implicating silica fillers (previously considered inert) as the probable cause for this behavioral divergence. A case study is presented wherein the application of the aforementioned FTIR technique fails to predict the durability of the coating system as a whole. The exploitation of the ultra-fast optical phenomenon of femtosecond (10-15S) laser ablation is studied as a potential tool to facilitate spectroscopic depth profiling of composite materials. Finally, the interferometric technique of Phase Shifting was evaluated as a potential high-sensitivity technique applied to the problem of determining internal stress evolution in curing and aging coatings.

European Scientific Notes. Volume 36, Number 11.

DTIC Science & Technology

1982-11-30

and polyisocyanides appear to by S. Piccarolo (Univ. of Palermo , Italy) of the be unique in their behavior in solution, thermal expansion of...of solvent down polyethylenes was investigated by D. Curto an activity gradient coupled with time- (Univ. of Palermo , Italy). When the rheo- dependent...ambitious in Paris. Projects are projected to start in program for a number of reasons, which were 1983 in Pakistan, India, Colombia , and Saudi discussed

High-performance liquid chromatography with nuclear magnetic resonance detection applied to organosilicon polymers. Part 2. Comparison with other methods.

PubMed

Blechta, Vratislav; Kurfürst, Milan; Sýkora, Jan; Schraml, Jan

2007-03-23

LC-NMR utilizing (1)H and (29)Si NMR spectroscopy is ideally suited for the analysis of silicones. It is shown that reversed phase gradient LC-NMR surpasses standard gel permeation chromatography (GPC) and diffusion ordered spectroscopy (DOSY) in the analysis of model hydride terminated polydimethylsiloxane. (1)H and (29)Si NMR in the stopped-flow arrangement leads to full identification of the components. Concentration gradient introduces a dependence of the (29)Si shifts on solvent composition, this dependence can be substantially reduced by a proposed method of referencing. It is shown that the ADEQUATE version of powerful but insensitive 2D INADEQUATE experiment can be used for complete line assignment.

Low-density resin impregnated ceramic article and method for making the same

NASA Technical Reports Server (NTRS)

Tran, Huy K. (Inventor); Henline, William D. (Inventor); Hsu, Ming-ta S. (Inventor); Rasky, Daniel J. (Inventor); Riccitiello, Salvatore R. (Inventor)

1997-01-01

A low-density resin impregnated ceramic article advantageously employed as a structural ceramic ablator comprising a matrix of ceramic fibers. The fibers of the ceramic matrix are coated with an organic resin film. The organic resin can be a thermoplastic resin or a cured thermosetting resin. In one embodiment, the resin is uniformly distributed within the ceramic article. In a second embodiment, the resin is distributed so as to provide a density gradient along at least one direction of the ceramic article. The resin impregnated ceramic article is prepared by providing a matrix of ceramic fibers; immersing the matrix of ceramic fibers in a solution of a solvent and an organic resin infiltrant; and removing the solvent to form a resin film on the ceramic fibers.

Crystal morphology optimization of thiamine hydrochloride in solvent system: Experimental and molecular dynamics simulation studies

NASA Astrophysics Data System (ADS)

Yang, Yang; Han, Dandan; Du, Shichao; Wu, Songgu; Gong, Junbo

2018-01-01

Thiamine hydrochloride (THCL) was produced in methanol accompanied with agglomeration in industry, the plate like morphology of THCL in methanol was not deserve to have a good quality. Selecting a suitable solvent should be considered because solvent could be one of the essential factors to impact morphology. Methanol and methanol/ethyl acetate solvent (0.2 vol fraction of methanol) was selected as the solvent system in reactive crystallization of THCL. The experiment results show the THCL crystal morphology in methanol/ethyl acetate solvent system was granular and more regular than that in methanol. In order to explicate the different crystal morphology in different solvents, molecular dynamics (MD) simulation was introduced to simulate crystal morphology in different solvents. The attachment energy (AE) model was employed to investigate the morphology of THCL under vacuum conditions, methanol and methanol/ethyl acetate solvent conditions, respectively. The simulation crystal morphology was in a good agreement with that of experimented. The particle of THCL in methanol/ethyl acetate solvent has less tendency to agglomeration, and then it is favorable to the downstream process, such as filtration, storage and transportation.

Identification and determination of the saikosaponins in Radix bupleuri by accelerated solvent extraction combined with rapid-resolution LC-MS.

PubMed

Yang, Yun-Yun; Tang, You-Zhi; Fan, Chun-Lin; Luo, Hui-Tai; Guo, Peng-Ran; Chen, Jian-Xin

2010-07-01

A method based on accelerated solvent extraction combined with rapid-resolution LC-MS for efficient extraction, rapid separation, online identification and accurate determination of the saikosaponins (SSs) in Radix bupleuri (RB) was developed. The RB samples were extracted by accelerated solvent extraction using 70% aqueous ethanol v/v as solvent, at a temperature of 120 degrees C and pressure of 100 bar, with 10 min of static extraction time and three extraction cycles. Rapid-resolution LC separation was performed by using a C(18) column at gradient elution of water (containing 0.5% formic acid) and acetonitrile, and the major constituents were well separated within 20 min. A TOF-MS and an IT-MS were used for online identification of the major constituents, and 27 SSs were identified or tentatively identified. Five major bioactive SSs (SSa, SSc, SSd, 6''-O-acetyl-SSa and 6''-O-acetyl-SSd) with obvious peak areas and good resolution were chosen as benchmark substances, and a triple quadrupole MS operating in multiple-reaction monitoring mode was used for their quantitative analysis. A total of 16 RB samples from different regions of China were analyzed. The results indicated that the method was rapid, efficient, accurate and suitable for use in the quality control of RB.

Analysis of flavonoids from lotus (Nelumbo nucifera) leaves using high performance liquid chromatography/photodiode array detector tandem electrospray ionization mass spectrometry and an extraction method optimized by orthogonal design.

PubMed

Chen, Sha; Wu, Ben-Hong; Fang, Jin-Bao; Liu, Yan-Ling; Zhang, Hao-Hao; Fang, Lin-Chuan; Guan, Le; Li, Shao-Hua

2012-03-02

The extraction protocol of flavonoids from lotus (Nelumbo nucifera) leaves was optimized through an orthogonal design. The solvent was the most important factor comparing solvent, solvent:tissue ratio, extraction time, and temperature. The highest yield of flavonoids was achieved with 70% methanol-water and a solvent:tissue ratio of 30:1 at 4 °C for 36 h. The optimized analytical method for HPLC was a multi-step gradient elution using 0.5% formic acid (A) and CH₃CN containing 0.1% formic acid (B), at a flow rate of 0.6 mL/min. Using this optimized method, thirteen flavonoids were simultaneously separated and identified by high performance liquid chromatography coupled with photodiode array detection/electrospray ionization mass spectrometry (HPLC/DAD/ESI-MS(n)). Five of the bioactive compounds are reported in lotus leaves for the first time. The flavonoid content of the leaves of three representative cultivars was assessed under the optimized extraction and HPLC analytical conditions, and the seed-producing cultivar 'Baijianlian' had the highest flavonoid content compared with rhizome-producing 'Zhimahuoulian' and wild floral cultivar 'Honglian'. Copyright © 2012 Elsevier B.V. All rights reserved.

An interesting two-phase solvent system and its use in preparative isolation of aconitines from aconite roots by counter-current chromatography.

PubMed

Han, Quan-Bin; Tang, Wai-Lun; Dong, Cai-Xia; Xu, Hong-Xi; Jiang, Zhi-Hong

2013-04-01

Two-phase solvent system plays crucial role in successful separation of organic compounds using counter-current chromatography (CCC). An interesting two-phase solvent system, composed of chloroform/ethyl acetate/methanol/water, is reported here, in which both phases contain sufficient organic solvents to balance their dissolving capacities. Adjusting the solvent system to get satisfactory partition coefficients (K values) for target compounds becomes relatively simple. This solvent system succeeded in sample preparation of aconitine (8.07 mg, 93.69%), hypaconitine (7.74 mg, 93.17%), mesaconitine (1.95 mg, 94.52%) from raw aconite roots (102.24 mg, crude extract), benzoylmesaconine (34.79 mg, 98.67%) from processed aconite roots (400.01 mg, crude extract), and yunaconitine (253.59 mg, 98.65%) from a crude extract of Aconitum forrestii (326.69 mg, crude extract). © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Enzymatic synthesis of esculin ester in ionic liquids buffered with organic solvents.

PubMed

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

2009-05-13

The enzymatic esterification of esculin catalyzed by Candida antarctica lipase B (Novozym 435) was carried out in ionic liquid (IL)-organic solvent mixed systems in comparison with individual systems. The reaction behaviors in IL-organic solvents were systemically evaluated using acetone as a model solvent. With organic solvents as media, the esterification rates of esculin depended mainly on its solubility in solvents; for the reactions in ILs, the reaction rates were generally low, and the anion part of the IL played a critical role in enzyme activity. Therefore, the esterification of esculin in IL-acetone mixtures made it possible to improve the solubility of esculin while the effects of ILs on lipase activity were minimized. Following the benignity of ILs to lipase activity, the anions of ILs were ranked in the order as [Tf(2)N](-) > [PF(6)](-) > [BF(4)](-) > [CF(3)SO(3)](-) > [C(4)F(9)SO(3)](-) > [TAF](-) > [MDEGSO(4)](-) > [OctSO(4)](-) > [ES](-) = [DMP](-) = [OTs](- )= Cl(-). The reaction behaviors differed in different systems and largely depended on the properties of the ILs and organic solvents. In general, improvements were observed in terms of both solubility and reaction efficiency. The knowledge acquired in this work gives a better understanding of multiple interactions in IL-organic solvent systems, which provide guidance for system design and optimization.

Efficacy of two rotary retreatment systems in removing Gutta-percha and sealer during endodontic retreatment with or without solvent: A comparative in vitro study

PubMed Central

Bhagavaldas, Moushmi Chalakkarayil; Diwan, Abhinav; Kusumvalli, S.; Pasha, Shiraz; Devale, Madhuri; Chava, Deepak Chowdary

2017-01-01

Objectives: The aim of this in vitro study was to compare the efficacy of two retreatment rotary systems in the removal of Gutta-percha (GP) and sealer from the root canal walls with or without solvent. Materials and Methods: Forty-eight extracted human mandibular first premolars were prepared and obturated with GP and AH Plus sealer. Samples were then randomly divided into four groups. Group I was retreated with MtwoR rotary system without solvent, Group II was retreated with MtwoR rotary system with Endosolv R as the solvent, Group III with D-RaCe rotary system without solvent, and Group IV with D-RaCe rotary system and Endosolv R solvent. The cleanliness of canal walls was determined by stereomicroscope (×20) and AutoCAD software. Kruskal–Wallis test and Mann–Whitney U-test were used to compare the data. Results: Results showed that none of the retreatment systems used in this study was able to completely remove the root canal filling material. D-RaCe with or without solvent showed significantly (P > 0.05) less filling material at all levels compared to MtwoR with/without solvent. Conclusion: Within the limitation of the current study, D-RaCe rotary retreatment system is more effective in removing filling material from root canal walls when compared to MtwoR rotary retreatment system. PMID:28761246

The Biodegradation of TNT in Enhanced Soil and Compost Systems

DTIC Science & Technology

1978-01-01

dimethylsulfoxide ( DMSO ) Is substituted for EDA because EDA tends to clog the sprayei . Dr. Chandler’s solvent system No. 1 is used for non-polar separa...material was converted to non- solvent -extractable, water-soluble materials of unknown Identity. These materials may represent the contents of dead... solvent system No. 1 54 2A TLC separation of TNT and derivatives using ChandlerIs solvent system No. 2 55 3A TLC separation of TNT and derivatives using

Ion-dipole interactions in concentrated organic electrolytes.

PubMed

Chagnes, Alexandre; Nicolis, Stamatios; Carré, Bernard; Willmann, Patrick; Lemordant, Daniel

2003-06-16

An algorithm is proposed for calculating the energy of ion-dipole interactions in concentrated organic electrolytes. The ion-dipole interactions increase with increasing salt concentration and must be taken into account when the activation energy for the conductivity is calculated. In this case, the contribution of ion-dipole interactions to the activation energy for this transport process is of the same order of magnitude as the contribution of ion-ion interactions. The ion-dipole interaction energy was calculated for a cell of eight ions, alternatingly anions and cations, placed on the vertices of an expanded cubic lattice whose parameter is related to the mean interionic distance (pseudolattice theory). The solvent dipoles were introduced randomly into the cell by assuming a randomness compacity of 0.58. The energy of the dipole assembly in the cell was minimized by using a Newton-Raphson numerical method. The dielectric field gradient around ions was taken into account by a distance parameter and a dielectric constant of epsilon = 3 at the surfaces of the ions. A fair agreement between experimental and calculated activation energy has been found for systems composed of gamma-butyrolactone (BL) as solvent and lithium perchlorate (LiClO4), lithium tetrafluoroborate (LiBF4), lithium hexafluorophosphate (LiPF6), lithium hexafluoroarsenate (LiAsF6), and lithium bis(trifluoromethylsulfonyl)imide (LiTFSI) as salts.

Effects of Anion Mobility on Electrochemical Behaviors of Lithium–Sulfur Batteries

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

Han, Kee Sung; Chen, Junzheng; Cao, Ruiguo

The electrolyte is a crucial component of lithium-sulfur (Li-S) batteries, as it controls polysulfide dissolution, charge shuttling processes, and solid-electrolyte interphase (SEI) layer formation. Experimentally, the overall performance of Li-S batteries varies with choice of solvent system and Li-salt used in the electrolyte, and a lack of predictive understanding about the effects of individual electrolyte components inhibits the rational design of electrolytes for Li-S batteries. Here we analyze the role of the counter anions of common Li salts (such as TfO-, FSI-, TFSI-, and TDI-) when dissolved in DOL/DME (1:1 vol.) for use in Li-S batteries. The evolution of ion-ionmore » and ion-solvent interactions due to vari-ous anions was analyzed using 17O NMR and pulsed-field gradient (PFG) NMR and then correlated with electrochemi-cal performance in Li-S cells. These data reveal that the for-mation of the passivation layer on the anode and the loss of active materials from the cathode (evidenced by polysulfide dissolution) are related to anion mobility and affinity with lithium polysulfide, respectively. For future electrolyte de-sign, anions with lower mobility and weaker interactions with lithium polysulfides may be superior candidates for increasing the long-term stability of Li-S batteries.« 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.

Use of an online extraction liquid chromatography quadrupole time-of-flight tandem mass spectrometry method for the characterization of polyphenols in Citrus paradisi cv. Changshanhuyu peel.

PubMed

Tong, Chaoying; Peng, Mijun; Tong, Runna; Ma, Ruyi; Guo, Keke; Shi, Shuyun

2018-01-19

Chemical profiling of natural products by high performance liquid chromatography (HPLC) was critical for understanding of their clinical bioactivities, and sample pretreatment steps have been considered as a bottleneck for analysis. Currently, concerted efforts have been made to develop sample pretreatment methods with high efficiency, low solvent and time consumptions. Here, a simple and efficient online extraction (OLE) strategy coupled with HPLC-diode array detector-quadrupole time-of-flight tandem mass spectrometry (HPLC-DAD-QTOF-MS/MS) was developed for rapid chemical profiling. For OLE strategy, guard column inserted with ground sample (2 mg) instead of sample loop was connected with manual injection valve, in which components were directly extracted and transferred to HPLC-DAD-QTOF-MS/MS system only by mobile phase without any extra time, solvent, instrument and operation. By comparison with offline heat-reflux extraction of Citrus paradisi cv. Changshanhuyu (Changshanhuyu) peel, OLE strategy presented higher extraction efficiency perhaps because of the high pressure and gradient elution mode. A total of twenty-two secondary metabolites were detected according to their retention times, UV spectra, exact mass, and fragmentation ions in MS/MS spectra, and nine of them were discovered in Changshanhuyu peel for the first time to our knowledge. It is concluded that the developed OLE-HPLC-DAD-QTOF-MS/MS system offers new perspectives for rapid chemical profiling of natural products. Copyright © 2017 Elsevier B.V. All rights reserved.

Online extraction-high performance liquid chromatography-diode array detector-quadrupole time-of-flight tandem mass spectrometry for rapid flavonoid profiling of Fructus aurantii immaturus.

PubMed

Tong, Runna; Peng, Mijun; Tong, Chaoying; Guo, Keke; Shi, Shuyun

2018-03-01

Chemical profiling of natural products by high performance liquid chromatography (HPLC) was critical for understanding of their clinical bioactivities, and sample pretreatment steps have been considered as a bottleneck for analysis. Currently, concerted efforts have been made to develop sample pretreatment methods with high efficiency, low solvent and time consumptions. Here, a simple and efficient online extraction (OLE) strategy coupled with HPLC-diode array detector-quadrupole time-of-flight tandem mass spectrometry (HPLC-DAD-QTOF-MS/MS) was developed for rapid chemical profiling. For OLE strategy, guard column inserted with ground sample (2 mg) instead of sample loop was connected with manual injection valve, in which components were directly extracted and transferred to HPLC-DAD-QTOF-MS/MS system only by mobile phase without any extra time, solvent, instrument and operation. By comparison with offline heat-reflux extraction for Fructus aurantii immaturus (Zhishi), OLE strategy presented higher extraction efficiency perhaps because of the high pressure and gradient elution mode. A total of eighteen flavonoids were detected according to their retention times, UV spectra, exact mass, and fragmentation ions in MS/MS spectra, and compound 9, natsudaidain-3-O-glucoside, was discovered in Zhishi for the first time. It is concluded that the developed OLE-HPLC-DAD-QTOF-MS/MS system offers new perspectives for rapid chemical profiling of natural products. Copyright © 2018. Published by Elsevier B.V.

Solvent-Induced Crystallization in Poly(Ethylene Terephthalate) during Mass Transport

NASA Astrophysics Data System (ADS)

Ouyang, Hao

2001-03-01

The solvent transport in poly(ethylene terephthalate) (PET) and related phase transformation were investigated. The data of mass sorption were analyzed according to Harmon¡¦s model for Case I (Fickian), Case II (swelling) and anomalous transport. This transport process in PET is accompanied by the induced crystallization of the original amorphous state. The transformation was studied by wide angle x-ray scattering (WAXS), small angle x-ray scattering (SAXS), Differential Scanning Calorimeter (DSC), density gradient column, and Fourier Transform Infra-Red (FTIR). During this process, the matrix is under a compressive strain that causes different kinetic path of crystallization as compared to that by thermal annealing. This state of strain will assist the development of the solvent-induced crystallization. It also can be explained in terms of the principle of Le Chatelier if the local equilibrium is assumed. The model regarding the crystallization was proposed in terms of the study of long period L, the crystal thickness lc and the thickness of amorphous layer la, obtained from the linear correlation function and interface distribution function.

Evolution in miniaturized column liquid chromatography instrumentation and applications: An overview.

PubMed

Nazario, Carlos E D; Silva, Meire R; Franco, Maraíssa S; Lanças, Fernando M

2015-11-20

The purpose of this article is to underline the miniaturized LC instrumental system and describe the evolution of commercially available systems by discussing their advantages and drawbacks. Nowadays, there are already many miniaturized LC systems available with a great variety of pump design, interface and detectors as well as efficient columns technologies and reduced connections devices. The solvent delivery systems are able to drive the mobile phase without flow splitters and promote gradient elution using either dual piston reciprocating or syringe-type pumps. The mass spectrometry as detection system is the most widely used detection system; among many alternative ionization sources direct-EI LC-MS is a promising alternative to APCI. In addition, capillary columns are now available showing many possibilities of stationary phases, inner diameters and hardware materials. This review provides a discussion about miniaturized LC demonstrating fundamentals and instrumentals' aspects of the commercially available miniaturized LC instrumental system mainly nano and micro LC formats. This review also covers the recent developments and trends in instrumentation, capillary and nano columns, and several applications of this very important and promising field. Copyright © 2015 Elsevier B.V. All rights reserved.

Development of solvent systems with room temperature ionic liquids for the countercurrent chromatographic separation of very nonpolar lipid compounds.

PubMed

Müller, Marco; Englert, Michael; Earle, Martyn J; Vetter, Walter

2017-03-10

Solvent systems are not readily available for the separation of very nonpolar compounds by countercurrent chromatography (CCC). In this study we therefore evaluated the suitability of room temperature ionic liquids (IL) in organic solvents for the CCC separation of the extremely nonpolar lipid compounds tripalmitin (PPP) and cholesteryl stearate (CS). The four IL tested were [C 10 mim][OTf], [C 2 mim][NTf 2 ], [P66614][NTf 2 ], and [P66614][Cl]. Search for a CCC-suited solvent system started with solubility studies with fourteen organic solvents. Following this, combinations were made with one organic solvent miscible and one organic solvent immiscible with IL (147 combinations). Twenty-four initially monophasic mixtures of two organic solvents became biphasic by adding IL. Several unexpected results could be observed. For instance, n-hexane and n-heptane became biphasic with [P66614][Cl]. Further nine systems became biphasic although the IL was not miscible in any of the two components. These 33 solvent systems were investigated with regard to phase ratio, settling time, share of IL in the upper phase and last not least the K U/L values of PPP and CS, which were 8.1 and 7.7 respectively. The most promising system, n-heptane/chloroform/[C 10 mim][OTf] (3:3:1, v/v/v) allowed a partial separation of PPP and CS by CCC which was not achieved beforehand. Copyright © 2017 Elsevier B.V. All rights reserved.

Aqueous Reversed-Phase HPLC/FT-IR Using Diffuse Reflectance Detections

NASA Astrophysics Data System (ADS)

Kalasinsky, Victor F.; Pai, T. H.; Kenton, R. C.; Kalasinsky, Kathryn S.

1989-12-01

Solvent-elimination HPLC/FT-IR has become a viable combination of two important techniques, and we have been developing a system which is adaptable to both normal and reversed-phase liquid chromatography. The interface involves the deposition of HPLC eluites onto a KCI-laden train with subsequent analysis via diffuse reflectance spectroscopy, and with minor modifications, the system can be used with microbore and analytical columns. With aqueous solvents, the water is converted to methanol and acetone in a post-column reaction with 2,2-dimethoxypropane before the eluites are deposited. A number of different samples have been used to demonstrate the interface and its flexibility. Steroids, analgesics, and other pharmaceutical preparations have been separated with reverse-phase solvents and identified by their infrared spectra. For some of the compounds studied, different infrared spectra of a given compound have been found to exhibit intensity variations, which arise from different crystalline states. The differences can be concentration dependent and may be useful in obtaining semi-quantitative information from the infrared spectra. Applications involving both gradient elution and isocratic separations have been successful. The former provides the same advantages for HPLC/FT-IR as one finds in conventional HPLC. More recent work has been applied to the use of buffers such as those frequently used in bioanalytical separations. In trying to simplify the post-column reaction with water, we have immobilized dehydration reagents onto silica particles and packed these materials into a column which is inserted in-line after the analytical column. Of the reagents utilized to date, 3,3-dimethoxypropyltrimethoxysilane has been found to perform most efficiently. It has advantages over the simpler reagents because it can be regenerated in the reaction column. Results and the efficiency of the dehydration process and its relation to the type of reagent and its coverage will be discussed.

An Improved Approach for Analyzing the Oxygen Compatibility of Solvents and other Oxygen-Flammable Materials for Use in Oxygen Systems

NASA Technical Reports Server (NTRS)

Harper, Susan A.; Juarez, Alfredo; Peralta, Stephen F.; Stoltzfus, Joel; Arpin, Christina Pina; Beeson, Harold D.

2016-01-01

Solvents used to clean oxygen system components must be assessed for oxygen compatibility, as incompatible residue or fluid inadvertently left behind within an oxygen system can pose a flammability risk. The most recent approach focused on solvent ignition susceptibility to assess the flammability risk associated with these materials. Previous evaluations included Ambient Pressure Liquid Oxygen (LOX) Mechanical Impact Testing (ASTM G86) and Autogenous Ignition Temperature (AIT) Testing (ASTM G72). The goal in this approach was to identify a solvent material that was not flammable in oxygen. As environmental policies restrict the available options of acceptable solvents, it has proven difficult to identify one that is not flammable in oxygen. A more rigorous oxygen compatibility approach is needed in an effort to select a new solvent for NASA applications. NASA White Sands Test Facility proposed an approach that acknowledges oxygen flammability, yet selects solvent materials based on their relative oxygen compatibility ranking, similar to that described in ASTM G63-99. Solvents are selected based on their ranking with respect to minimal ignition susceptibility, damage and propagation potential, as well as their relative ranking when compared with other solvent materials that are successfully used in oxygen systems. Test methods used in this approach included ASTM G86 (Ambient Pressure LOX Mechanical Impact Testing and Pressurized Gaseous Oxygen (GOX) Mechanical Impact Testing), ASTM G72 (AIT Testing), and ASTM D240 (Heat of Combustion (HOC) Testing). Only four solvents were tested through the full battery of tests for evaluation of oxygen compatibility: AK-225G as a baseline comparison, Solstice PF, L-14780, and Vertrel MCA. Baseline solvent AK-225G exhibited the lowest HOC and highest AIT of solvents tested. Nonetheless, Solstice PF, L-14780, and Vertrel MCA HOCs all fell well within the range of properties that are associated with proven oxygen system materials. Tested AITs for these solvents fell only slightly lower than the AIT for the proven AK-225G solvent. Based on these comparisons in which solvents exhibited properties within those ranges seen with proven oxygen system materials, it is believed that Solstice PF, L-14780, and Vertrel MCA would perform well with respect to oxygen compatibility.

Effective temperatures of hot Brownian motion.

PubMed

Falasco, G; Gnann, M V; Rings, D; Kroy, K

2014-09-01

We derive generalized Langevin equations for the translational and rotational motion of a heated Brownian particle from the fluctuating hydrodynamics of its nonisothermal solvent. The temperature gradient around the particle couples to the hydrodynamic modes excited by the particle itself so that the resulting noise spectrum is governed by a frequency-dependent temperature. We show how the effective temperatures at which the particle coordinates and (angular) velocities appear to be thermalized emerge from this central quantity.

Processing Solvent Dependent Morphology of Diketopyrrolopyrrole (DPP) based Low Band Gap Polymer and PCBM Blends

NASA Astrophysics Data System (ADS)

Ferdous, Sunzida; Liu, Feng; Russell, Thomas

2013-03-01

Solution processing of polymer semiconductors is widely used for fabrication of low cost organic solar cells. Recently, mixed solvent systems or additive based systems for fabricating polymer solar cells have proven to be beneficial for obtaining high performance devices with multi-length scale morphologies. To control the morphology during the processing step, one needs to understand the effect of solvent as it evaporates to form the final thin film structure. In this study, we used diketopyrrolopyrrole (DPP) based low band gap polymer and phenyl-C71-butyric acid methyl ester (PCBM) blend in a series of mixed solvent systems consisting of a good solvent for both of the active material components, as well as different solvents that are good solvents for PCBM, but poor solvents for the polymer. Different evaporation times of the poor solvents during the drying process, and different solubility of the polymer in these poor solvents as well as their interaction with the substrate play an important role in the final morphology. In-situ GIWAXS studies were performed to observe the evolution of the structure as the solvent evaporates. The final morphologies of the thin film devices were also characterized by AFM, TEM, and various x-ray scattering techniques to correlate the morphology with the obtained device performances.

Nutritional Composition and Phytochemical, Antioxidative, and Antifungal Activities of Pergularia tomentosa L.

PubMed Central

Belghith, Hafedh; Ben Abdallah, Ferjani; Belghith, Karima

2017-01-01

Crude extracts from a medicinal Tunisian plant, Pergularia tomentosa L., were the investigated natural material. Butanolic extract of roots analyzed with IR spectra revealed the presence of hydroxyl, alcoholic, and carboxylic groups and sugars units. Analysis of some secondary metabolites, total phenolic, flavonoids, flavonols, and procyanidins, was performed using different solvents following the increased gradient of polarity. Fruits and leaves contained the highest amounts of all these compounds. Antioxidant properties were evaluated by the determination of free radical scavenging activity and the reducing power of methanolic extracts. Fruits and leaf extracts were the most powerful antioxidants for the two-assay in vitro system. Stems and fruits extracts exhibit an antifungal activity against Fusarium oxysporum f. sp. lycopersici which could become an alternative to synthetic fungicide to control Solanum species fungal diseases. PMID:28409159

Group extraction of organic compounds present in liquid samples

NASA Technical Reports Server (NTRS)

Jahnsen, Vilhelm J. (Inventor)

1976-01-01

An extraction device is disclosed comprising a tube containing a substantially inert, chemically non-reactive packing material with a large surface area to volume ratio. A sample which consists of organic compounds dissolved in a liquid, is introduced into the tube. As the sample passes through the packing material it spreads over the material's large surface area to form a thin liquid film which is held on the packing material in a stationary state. A particular group or family of compounds is extractable from the sample by passing a particular solvent system consisting of a solvent and selected reagents through the packing material. The reagents cause optimum conditions to exist for the compounds of the particular family to pass through the phase boundary between the sample liquid and the solvent of the solvent system. Thus, the compounds of the particular family are separated from the sample liquid and become dissolved in the solvent of the solvent system. The particular family of compounds dissolved in the solvent, representing an extract, exits the tube together with the solvent through the tube's nozzle, while the rest of the sample remains on the packing material in a stationary state. Subsequently, a different solvent system may be passed through the packing material to extract another family of compounds from the remaining sample on the packing material.

Ion conducting fluoropolymer carbonates for alkali metal ion batteries

DOEpatents

DeSimone, Joseph M.; Pandya, Ashish; Wong, Dominica; Balsara, Nitash P.; Thelen, Jacob; Devaux, Didier

2017-09-05

Liquid or solid electrolyte compositions are described that comprise a homogeneous solvent system and an alkali metal salt dissolved in said solvent system. The solvent system may comprise a fluoropolymer, having one or two terminal carbonate groups covalently coupled thereto. Batteries containing such electrolyte compositions are also described.

Control of Chemical Equilibrium by Solvent: A Basis for Teaching Physical Chemistry of Solutions

ERIC Educational Resources Information Center

Prezhdo, Oleg V.; Craig, Colleen F.; Fialkov, Yuriy; Prezhdo, Victor V.

2007-01-01

The study demonstrates that the solvent present in a system can highly alter and control the chemical equilibrium of a system. The results show that the dipole moment and polarizibility of a system can be highly altered by using different mixed solvents.

Treatment System for Removing Halogenated Compounds from Contaminated Sources

NASA Technical Reports Server (NTRS)

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

2015-01-01

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

Low Density Resin Impregnated Ceramic Article Having an Average Density of 0.15 to 0.40 G/CC

NASA Technical Reports Server (NTRS)

Tran, Huy K. (Inventor); Henline, William D. (Inventor); Hsu, Ming-ta S. (Inventor); Rasky, Daniel J. (Inventor); Riccitiello, Salvatore R. (Inventor)

1996-01-01

A low-density resin impregnated ceramic article advantageously employed as a structural ceramic ablator comprising a fired preform of ceramic fibers. The fibers of the ceramic preform are coated with an organic resin film. The organic resin can be a thermoplastic resin or a cured thermosetting resin. In one embodiment, the resin is uniformly distributed within the ceramic article. In a second embodiment, the resin is distributed so as to provide a density gradient along at least one direction of the ceramic article. The resin impregnated ceramic article is prepared by providing a fired preform of ceramic fibers; immersing the preform of ceramic fibers in a solution of a solvent and an organic resin infiltrant; and removing the solvent to form a resin film on the ceramic fibers.

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

PubMed

Jinno, Naoya; Hashimoto, Masahiko; Tsukagoshi, Kazuhiko

2011-01-01

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

Lipase mediated synthesis of rutin fatty ester: Study of its process parameters and solvent polarity.

PubMed

Vaisali, C; Belur, Prasanna D; Regupathi, Iyyaswami

2017-10-01

Lipophilization of antioxidants is recognized as an effective strategy to enhance solubility and thus effectiveness in lipid based food. In this study, an effort was made to optimize rutin fatty ester synthesis in two different solvent systems to understand the influence of reaction system hydrophobicity on the optimum conditions using immobilised Candida antartica lipase. Under unoptimized conditions, 52.14% and 13.02% conversion was achieved in acetone and tert-butanol solvent systems, respectively. Among all the process parameters, water activity of the system was found to show highest influence on the conversion in each reaction system. In the presence of molecular sieves, the ester production increased to 62.9% in tert-butanol system, unlike acetone system. Under optimal conditions, conversion increased to 60.74% and 65.73% in acetone and tert-butanol system, respectively. This study shows, maintaining optimal water activity is crucial in reaction systems having polar solvents compared to more non-polar solvents. Copyright © 2017 Elsevier Ltd. All rights reserved.

ODC-Free Solvent Implementation Issues for Vulcanized Rubber and Bond Systems

NASA Technical Reports Server (NTRS)

Hodgson, James R.; McCool, Alex (Technical Monitor)

2001-01-01

Thiokol Propulsion has worked extensively to replace 1,1,1-trichloroethane (TCA) with ozone depleting chemicals (ODC)-free solvents for use in the manufacture of the Reusable Solid Rocket Motor (RSRM) for the Space Shuttle Program. As Thiokol has transitioned from sub-scale to full-scale testing and implementation of these new solvents, issues have been discovered which have required special attention. The original intent of Thiokol's solvent replacement strategy was to replace TCA with a single drop-in solvent for all equivalent applications. We have learned that a single candidate does not exist for replacing TCA. Solvent incompatibility with process materials has caused us to seek for niche solvents and/or processing changes that provide an ODC-free solution for special applications. This paper addresses some of the solvent incompatibilities, which have lead to processes changes and possible niche solvent usage. These incompatibilities were discovered during full-scale testing of ODC-free solvents and relate to vulcanized rubber and bond systems in the RSRM. Specifically, the following items are presented: (1) Cure effects of d-limonene based solvents on Silica Filled Ethylene Propylene Diene Monomer (SF-EPDM) rubber. During full-scale test operations, Thiokol discovered that d-limonene (terpene) based solvents inhibit the cure of EPDM rubber. Subsequent testing showed the same issue with Nitrile Butadiene Rubber (NBR). Also discussed are efforts to minimize uncured rubber exposure to solvents; and (2) Cured bond system sensitivity to ODC-free solvents. During full scale testing it was discovered that a natural rubber to steel vulcanized bond could degrade after prolonged exposure to ODC-free solvents. Follow on testing showed that low vapor pressure and residence time seemed to be most likely cause for failure.

Continuous gradient scaffolds for rapid screening of cell-material interactions and interfacial tissue regeneration.

PubMed

Bailey, Brennan M; Nail, Lindsay N; Grunlan, Melissa A

2013-09-01

In tissue engineering, the physical and chemical properties of the scaffold mediates cell behavior, including regeneration. Thus a strategy that permits rapid screening of cell-scaffold interactions is critical. Herein, we have prepared eight "hybrid" hydrogel scaffolds in the form of continuous gradients such that a single scaffold contains spatially varied properties. These scaffolds are based on combining an inorganic macromer (methacrylated star polydimethylsiloxane, PDMSstar-MA) and organic macromer (poly(ethylene glycol)diacrylate, PEG-DA) as well as both aqueous and organic fabrication solvents. Having previously demonstrated its bioactivity and osteoinductivity, PDMSstar-MA is a particularly powerful component to incorporate into instructive gradient scaffolds based on PEG-DA. The following parameters were varied to produce the different gradients or gradual transitions in: (1) the wt.% ratio of PDMSstar-MA to PEG-DA macromers, (2) the total wt.% macromer concentration, (3) the number average molecular weight (Mn) of PEG-DA and (4) the Mn of PDMSstar-MA. Upon dividing each scaffold into four "zones" perpendicular to the gradient, we were able to demonstrate the spatial variation in morphology, bioactivity, swelling and modulus. Among these gradient scaffolds are those in which swelling and modulus are conveniently decoupled. In addition to rapid screening of cell-material interactions, these scaffolds are well suited for regeneration of interfacial tissues (e.g. osteochondral tissues) that transition from one tissue type to another. Copyright © 2013 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Extraction of organic compounds with room temperature ionic liquids.

PubMed

Poole, Colin F; Poole, Salwa K

2010-04-16

Room temperature ionic liquids are novel solvents with a rather specific blend of physical and solution properties that makes them of interest for applications in separation science. They are good solvents for a wide range of compounds in which they behave as polar solvents. Their physical properties of note that distinguish them from conventional organic solvents are a negligible vapor pressure, high thermal stability, and relatively high viscosity. They can form biphasic systems with water or low polarity organic solvents and gases suitable for use in liquid-liquid and gas-liquid partition systems. An analysis of partition coefficients for varied compounds in these systems allows characterization of solvent selectivity using the solvation parameter model, which together with spectroscopic studies of solvent effects on probe substances, results in a detailed picture of solvent behavior. These studies indicate that the solution properties of ionic liquids are similar to those of polar organic solvents. Practical applications of ionic liquids in sample preparation include extractive distillation, aqueous biphasic systems, liquid-liquid extraction, liquid-phase microextraction, supported liquid membrane extraction, matrix solvents for headspace analysis, and micellar extraction. The specific advantages and limitations of ionic liquids in these studies is discussed with a view to defining future uses and the need not to neglect the identification of new room temperature ionic liquids with physical and solution properties tailored to the needs of specific sample preparation techniques. The defining feature of the special nature of ionic liquids is not their solution or physical properties viewed separately but their unique combinations when taken together compared with traditional organic solvents. Copyright 2009 Elsevier B.V. All rights reserved.

Entry into and Release of Solvents by Escherichia coli in an Organic-Aqueous Two-Liquid-Phase System and Substrate Specificity of the AcrAB-TolC Solvent-Extruding Pump

PubMed Central

Tsukagoshi, Norihiko; Aono, Rikizo

2000-01-01

Growth of Escherichia coli is inhibited upon exposure to a large volume of a harmful solvent, and there is an inverse correlation between the degree of inhibition and the log POW of the solvent, where POW is the partition coefficient measured for the partition equilibrium established between the n-octanol and water phases. The AcrAB-TolC efflux pump system is involved in maintaining intrinsic solvent resistance. We inspected the solvent resistance of ΔacrAB and/or ΔtolC mutants in the presence of a large volume of solvent. Both mutants were hypersensitive to weakly harmful solvents, such as nonane (log POW = 5.5). The ΔtolC mutant was more sensitive to nonane than the ΔacrAB mutant. The solvent entered the E. coli cells rapidly. Entry of solvents with a log POW higher than 4.4 was retarded in the parent cells, and the intracellular levels of these solvents were maintained at low levels. The ΔtolC mutant accumulated n-nonane or decane (log POW = 6.0) more abundantly than the parent or the ΔacrAB mutant. The AcrAB-TolC complex likely extrudes solvents with a log POW in the range of 3.4 to 6.0 through a first-order reaction. The most favorable substrates for the efflux system were considered to be octane, heptane, and n-hexane. PMID:10940021

Determination of flavonoids and saponins in Gynostemma pentaphyllum (Thunb.) Makino by liquid chromatography-mass spectrometry.

PubMed

Kao, T H; Huang, S C; Inbaraj, B Stephen; Chen, B H

2008-09-26

Gynostemma pentaphyllum (Thunb.) Makino, a traditional Chinese herb possessing antitumor and antioxidant activities, has been shown to contain several functional components like saponins and flavonoids. However, their identities remain uncertain. The objectives of this study were to develop an appropriate extraction, purification and HPLC-MS method to determine saponins and flavonoids in G. pentaphyllum. Both flavonoids and saponins were extracted with methanol, followed by purification with a C18 cartridge to elute the former with 50% methanol and the latter with 100% methanol. A total of 34 saponins were separated within 40 min by a Gemini C18 column and a gradient mobile phase of acetonitrile and 0.1% formic acid in water, in which 18 saponins were identified by LC-MS with ESI mode and Q-TOF (LC/MS/MS). Similarly, a total of eight flavonoids were separated within 45 min by the same column and a gradient solvent system of methanol and 0.1% formic acid in water, with identification being carried out by a post-column derivatization method and LC-MS with ESI mode. The amounts of flavonoids in G. pentaphyllum ranged from 170.7 to 2416.5 mug g(-1), whereas saponins were from 491.0 to 89,888.9 mug g(-1).

Quality by design approach for the separation of naproxcinod and its related substances by fused core particle technology column.

PubMed

Inugala, Ugandar Reddy; Pothuraju, Nageswara Rao; Vangala, Ranga Reddy

2013-01-01

This paper describes the development of a rapid, novel, stability-indicating gradient reversed-phase high-performance liquid chromatographic method and associated system suitability parameters for the analysis of naproxcinod in the presence of its related substances and degradents using a quality-by-design approach. All of the factors that affect the separation of naproxcinod and its impurities and their mutual interactions were investigated and robustness of the method was ensured. The method was developed using an Ascentis Express C8 150 × 4.6 mm, 2.7 µm column with a mobile phase containing a gradient mixture of two solvents. The eluted compounds were monitored at 230 nm, the run time was 20 min within which naproxcinod and its eight impurities were satisfactorily separated. Naproxcinod was subjected to the stress conditions of oxidative, acid, base, hydrolytic, thermal and photolytic degradation. Naproxcinod was found to degrade significantly in acidic and basic conditions and to be stable in thermal, photolytic, oxidative and aqueous degradation conditions. The degradation products were satisfactorily resolved from the primary peak and its impurities, proving the stability-indicating power of the method. The developed method was validated as per International Conference on Harmonization guidelines with respect to specificity, linearity, limit of detection, limit of quantification, accuracy, precision and robustness.

A novel accelerated in vitro release method to evaluate the release of thymopentin from PLGA microspheres.

PubMed

Xie, Xiangyang; Li, Zhiping; Zhang, Ling; Chi, Qiang; Yang, Yanfang; Zhang, Hui; Yang, Yang; Mei, Xingguo

2015-01-01

A novel accelerated method of good correlations with "real-time" release to evaluate in vitro thymopentin release from poly (D, L-lactide-co-glycolide) (PLGA) microsphere was developed. Thymopentin-loaded microspheres were made from three types of PLGA, and peptide release was studied in various conditions. Incomplete release of peptide (<60%) from microspheres was found in accelerated testing with two typical release media. This problem was circumvented by adding organic solvents to the release media and varying the temperature in the media heating process. Release media containing three kinds of organic solvents at 50 °C were tested, respectively, and hydro-alcoholic solution was selected for further study. After the surfactant concentration (0.06%, W/V) and ethanol concentration (20%, V/V) were fixed, a gradient heating program, consisting of three stages and each stage with a different temperature, was introduced to enhance the correlations between the short- and long-term release. After adjusting the heating time of each stage, a good correlation (R(2) = 9896, formulation 8 K; R(2) = 0.9898, formulation 13 K; R(2) = 0.9886, formulation 28 K) between accelerated and "real-time" release was obtained. By optimizing the conditions as ethanol concentration and temperature gradients, this accelerated method may be appropriate for similar peptide formulations that not well correlate with "real-time" release.

Chemical composition separation of a propylene-ethylene random copolymer by high temperature solvent gradient interaction chromatography.

PubMed

Liu, Yonggang; Phiri, Mohau Justice; Ndiripo, Anthony; Pasch, Harald

2017-11-03

A propylene-ethylene random copolymer was fractionated by preparative temperature rising elution fractionation (TREF). The structural heterogeneity of the bulk sample and its TREF fractions was studied by high temperature liquid chromatography with a solvent gradient elution from 1-decanol to 1,2,4-trichlorobenzene. HPLC alone cannot resolve those propylene-ethylene copolymers with high ethylene content in the bulk sample, due to their low weight fractions in the bulk sample and a small response factor of these components in the ELSD detector, as well as their broad chemical composition distribution. These components can only be detected after being separated and enriched by TREF followed by HPLC analysis. Chemical composition separations were achieved for TREF fractions with average ethylene contents between 2.1 and 22.0mol%, showing that copolymers with higher ethylene contents were adsorbed stronger in the Hypercarb column and eluted later. All TREF fractions, except the 40°C fraction, were relatively homogeneous in both molar mass and chemical composition. The 40°C fraction was rather broad in both molar mass and chemical composition distributions. 2D HPLC showed that the molar masses of the components containing more ethylene units were getting lower for the 40°C fraction. HPLC revealed and confirmed that co-crystallization influences the separation in TREF of the studied propylene-ethylene copolymer. Copyright © 2017 Elsevier B.V. All rights reserved.

SAGE 2.0 SOLVENT ALTERNATIVES GUIDE - USER'S GUIDE

EPA Science Inventory

The guide provides instruction for using the SAGE (Solvent Alternatives Guide) software system, version 2.O. It assumes that the user is familiar with the fundamentals of operating a personal computer under the Microsoft disk operating system (MS-DOS). AGE recommends solvent repl...

SAGE 2.1: SOLVENT ALTERNATIVES GUIDE: USER'S GUIDE

EPA Science Inventory

The guide provides instruction for using the SAGE (Solvent Alternatives GuidE) software system, version 2.1. SAGE recommends solvent replacements in cleaning and degreasing operations. It leads the user through a question-and-answer session. The user's responses allow the system ...

Effects of solvation on partition and dimerization of benzoic acid in mixed solvent systems.

PubMed

Yamada, H; Yajima, K; Wada, H; Nakagawa, G

1995-06-01

The partition of benzoic acid between 0.1M perchloric acid solution and two kinds of mixed solvents has been carried out at 25 degrees C. The partition and dimerization constants of benzoic acid have been determined in the 1-octanol-benzene and 2-octanone-benzene systems. In both the mixed solvent systems, with increasing content of 1-octanol and 2-octanone in each mixed solvent, the partition constant of benzoic acid has been found to increase, and the dimerization constant of benzoic acid in each organic phase to decrease. These phenomena are attributable to solvation of monomeric benzoic acid by 1-octanol and 2-octanone molecules in each mixed solvent.

Mechanistic principles of colloidal crystal growth by evaporation-induced convective steering.

PubMed

Brewer, Damien D; Allen, Joshua; Miller, Michael R; de Santos, Juan M; Kumar, Satish; Norris, David J; Tsapatsis, Michael; Scriven, L E

2008-12-02

We simulate evaporation-driven self-assembly of colloidal crystals using an equivalent network model. Relationships between a regular hexagonally close-packed array of hard, monodisperse spheres, the associated pore space, and selectivity mechanisms for face-centered cubic microstructure propagation are described. By accounting for contact line rearrangement and evaporation at a series of exposed menisci, the equivalent network model describes creeping flow of solvent into and through a rigid colloidal crystal. Observations concerning colloidal crystal growth are interpreted in terms of the convective steering hypothesis, which posits that solvent flow into and through the pore space of the crystal may play a major role in colloidal self-assembly. Aspects of the convective steering and deposition of high-Peclet-number rigid spherical particles at a crystal boundary are inferred from spatially resolved solvent flow into the crystal. Gradients in local flow through boundary channels were predicted due to the channels' spatial distribution relative to a pinned free surface contact line. On the basis of a uniform solvent and particle flux as the criterion for stability of a particular growth plane, these network simulations suggest the stability of a declining {311} crystal interface, a symmetry plane which exclusively propagates fcc microstructure. Network simulations of alternate crystal planes suggest preferential growth front evolution to the declining {311} interface, in consistent agreement with the proposed stability mechanism for preferential fcc microstructure propagation in convective assembly.

Effect of solvent evaporation and coagulation on morphology development of asymmetric membranes

NASA Astrophysics Data System (ADS)

Chandrasekaran, Neelakandan; Kyu, Thein

2008-03-01

Miscibility behavior of blends of amorphous polyamide (PA) and polyvinylpyrrolidone (PVP) was studied in relation to membrane formation. Dimethylsulfoxide (DMSO) and water were used as solvent and non-solvent, respectively. Differential scanning calorimetry and cloud point measurements revealed that the binary PA/PVP blends as well as the ternary PA/PVP/DMSO system were completely miscible at all compositions. However, the addition of non-solvent (water) to this ternary system has led to phase separation. Visual turbidity study was used to establish a ternary liquid-liquid phase diagram of the PA-PVP/DMSO/water system. Scanning Electron Microscopy (SEM) showed the development of finger-like and sponge-like cross sectional morphologies during coagulation. Effects of polymer concentration, PA/PVP blend ratio, solvent/non-solvent quality, and evaporation time on the resulting membrane morphology will be discussed.

Linear-scaling time-dependent density-functional theory beyond the Tamm-Dancoff approximation: Obtaining efficiency and accuracy with in situ optimised local orbitals.

PubMed

Zuehlsdorff, T J; Hine, N D M; Payne, M C; Haynes, P D

2015-11-28

We present a solution of the full time-dependent density-functional theory (TDDFT) eigenvalue equation in the linear response formalism exhibiting a linear-scaling computational complexity with system size, without relying on the simplifying Tamm-Dancoff approximation (TDA). The implementation relies on representing the occupied and unoccupied subspaces with two different sets of in situ optimised localised functions, yielding a very compact and efficient representation of the transition density matrix of the excitation with the accuracy associated with a systematic basis set. The TDDFT eigenvalue equation is solved using a preconditioned conjugate gradient algorithm that is very memory-efficient. The algorithm is validated on a small test molecule and a good agreement with results obtained from standard quantum chemistry packages is found, with the preconditioner yielding a significant improvement in convergence rates. The method developed in this work is then used to reproduce experimental results of the absorption spectrum of bacteriochlorophyll in an organic solvent, where it is demonstrated that the TDA fails to reproduce the main features of the low energy spectrum, while the full TDDFT equation yields results in good qualitative agreement with experimental data. Furthermore, the need for explicitly including parts of the solvent into the TDDFT calculations is highlighted, making the treatment of large system sizes necessary that are well within reach of the capabilities of the algorithm introduced here. Finally, the linear-scaling properties of the algorithm are demonstrated by computing the lowest excitation energy of bacteriochlorophyll in solution. The largest systems considered in this work are of the same order of magnitude as a variety of widely studied pigment-protein complexes, opening up the possibility of studying their properties without having to resort to any semiclassical approximations to parts of the protein environment.

Electrolyte Suitable for Use in a Lithium Ion Cell or Battery

NASA Technical Reports Server (NTRS)

McDonald, Robert C. (Inventor)

2014-01-01

Electrolyte suitable for use in a lithium ion cell or battery. According to one embodiment, the electrolyte includes a fluorinated lithium ion salt and a solvent system that solvates lithium ions and that yields a high dielectric constant, a low viscosity and a high flashpoint. In one embodiment, the solvent system includes a mixture of an aprotic lithium ion solvating solvent and an aprotic fluorinated solvent.

Preferential Solvation of an Asymmetric Redox Molecule

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

Han, Kee Sung; Rajput, Nav Nidhi; Vijayakumar, M.

2016-12-15

The fundamental correlations between inter-molecular interactions, solvation structure and functionality of electrolytes are in many cases unknown, particularly for multi-component liquid systems. In this work, we explore such correlations by investigating the complex interplay between solubility and solvation structure for the electrolyte system comprising N-(ferrocenylmethyl)-N,N-dimethyl-N-ethylammonium bistrifluoromethylsulfonimide (Fc1N112-TFSI) dissolved in a ternary carbonate solvent mixture using combined NMR relaxation and computational analyses. Probing the evolution of the solvent-solvent, ion-solvent and ion-ion interactions with an increase in solute concentration provides a molecular level understanding of the solubility limit of the Fc1N112-TFSI system. An increase in solute con-centration leads to pronounced Fc1N112-TFSI contact-ionmore » pair formation by diminishing solvent-solvent and ion-solvent type interactions. At the solubility limit, the precipitation of solute is initiated through agglomeration of contact-ion pairs due to overlapping solvation shells.« less

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.

Effects of solvent on solution prepregging of the resin system LaRC{trademark}-IAX-2

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

Cano, R.J.; Massey, C.P.; St. Clair, T.L.

1996-12-31

This work assesses the feasibility of using an alternative solvent for the production of composites from polyimide resin systems via solution prepregging. Previous work on solution prepregging of polyimide systems at NASA Langley Research Center has concentrated on the use of the solvent N-methylpyrrolidinone. An alternative solvent with a similar boiling point, -{gamma}-Butyrolactone, was used to prepare the poly(amide acid) version of LaRC{trademark}-IAX-2. These solutions were subsequently used to prepare prepreg and graphite-reinforced composites. Mechanical properties are presented for the resin system LaRC{trademark}-IAX-2 (4% and 5% offset in stoichiometry and endcapped with phthalic anhydride) impregnated onto Hercules IM7 carbon fiber.more » Results from this work were compared to data obtained on the same resin system which had been solution prepregged with the solvent N-methylpyrrolidinone.« less

An investigation into dispersion upon switching between solvents within a microfluidic system using a chemically resistant integrated optical refractive index sensor.

PubMed

Parker, Richard M; Gates, James C; Wales, Dominic J; Smith, Peter G R; Grossel, Martin C

2013-02-07

A planar Bragg grating device has been developed that is capable of detecting changes in the refractive index of a wide range of fluids including solvents, acids and bases. The integration of this high precision refractive index sensor within a chemically resistant microfluidic flow system has enabled the investigation of diverse fluid interactions. By cycling between different solvents, both miscible and immiscible, within the microfluidic system it is shown that the previous solvent determines the nature of the refractive index profile across the transition in composition. This solvent dispersion effect is investigated with particular attention to the methanol-water transition, where transients in refractive index are observed that are an order of magnitude larger in amplitude than the difference between the bulk fluids. The potential complications of such phenomenon are discussed together with an example of a device that exploits this effect for the unambiguous composition measurement of a binary solvent system.

Innovative polymeric system (IPS) for solvent-free lipophilic drug transdermal delivery via dissolving microneedles.

PubMed

Dangol, Manita; Yang, Huisuk; Li, Cheng Guo; Lahiji, Shayan Fakhraei; Kim, Suyong; Ma, Yonghao; Jung, Hyungil

2016-02-10

Lipophilic drugs are potential drug candidates during drug development. However, due to the need for hazardous organic solvents for their solubilization, these drugs often fail to reach the pharmaceutical market, and in doing so highlight the importance of solvent free systems. Although transdermal drug delivery systems (TDDSs) are considered prospective safe drug delivery routes, a system involving lipophilic drugs in solvent free or powder form has not yet been described. Here, we report, for the first time, a novel approach for the delivery of every kind of lipophilic drug in powder form based on an innovative polymeric system (IPS). The phase transition of powder form of lipophilic drugs due to interior chemical bonds between drugs and biodegradable polymers and formation of nano-sized colloidal structures allowed the fabrication of dissolving microneedles (DMNs) to generate a powerful TDDS. We showed that IPS based DMN with powder capsaicin enhances the therapeutic effect for treatment of the rheumatic arthritis in a DBA/1 mouse model compared to a solvent-based system, indicating the promising potential of this new solvent-free platform for lipophilic drug delivery. Copyright © 2016 Elsevier B.V. All rights reserved.

40 CFR 60.434 - Monitoring of operations and recordkeeping.

Code of Federal Regulations, 2012 CFR

2012-07-01

... affected facility using waterborne ink systems or solvent-borne ink systems with solvent recovery systems...) If affected facilities share the same raw ink storage/handling system with existing facilities...

40 CFR 60.434 - Monitoring of operations and recordkeeping.

Code of Federal Regulations, 2014 CFR

2014-07-01

... affected facility using waterborne ink systems or solvent-borne ink systems with solvent recovery systems...) If affected facilities share the same raw ink storage/handling system with existing facilities...

40 CFR 60.434 - Monitoring of operations and recordkeeping.

Code of Federal Regulations, 2013 CFR

2013-07-01

... affected facility using waterborne ink systems or solvent-borne ink systems with solvent recovery systems...) If affected facilities share the same raw ink storage/handling system with existing facilities...

Modeling of the phase equilibria of polystyrene in methylcyclohexane with semi-empirical quantum mechanical methods I.

PubMed

Wilczura-Wachnik, Hanna; Jónsdóttir, Svava Osk

2003-04-01

A method for calculating interaction parameters traditionally used in phase-equilibrium computations in low-molecular systems has been extended for the prediction of solvent activities of aromatic polymer solutions (polystyrene+methylcyclohexane). Using ethylbenzene as a model compound for the repeating unit of the polymer, the intermolecular interaction energies between the solvent molecule and the polymer were simulated. The semiempirical quantum chemical method AM1, and a method for sampling relevant internal orientations for a pair of molecules developed previously were used. Interaction energies are determined for three molecular pairs, the solvent and the model molecule, two solvent molecules and two model molecules, and used to calculated UNIQUAC interaction parameters, a(ij) and a(ji). Using these parameters, the solvent activities of the polystyrene 90,000 amu+methylcyclohexane system, and the total vapor pressures of the methylcyclohexane+ethylbenzene system were calculated. The latter system was compared to experimental data, giving qualitative agreement. Figure Solvent activities for the methylcylcohexane(1)+polystyrene(2) system at 316 K. Parameters aij (blue line) obtained with the AM1 method; parameters aij (pink line) from VLE data for the ethylbenzene+methylcyclohexane system. The abscissa is the polymer weight fraction defined as y2(x1)=(1mx1)M2/[x1M1+(1mx1)M2], where x1 is the solvent mole fraction and Mi are the molecular weights of the components.

Non-equilibrium reaction and relaxation dynamics in a strongly interacting explicit solvent: F + CD3CN treated with a parallel multi-state EVB model

NASA Astrophysics Data System (ADS)

Glowacki, David R.; Orr-Ewing, Andrew J.; Harvey, Jeremy N.

2015-07-01

We describe a parallelized linear-scaling computational framework developed to implement arbitrarily large multi-state empirical valence bond (MS-EVB) calculations within CHARMM and TINKER. Forces are obtained using the Hellmann-Feynman relationship, giving continuous gradients, and good energy conservation. Utilizing multi-dimensional Gaussian coupling elements fit to explicitly correlated coupled cluster theory, we built a 64-state MS-EVB model designed to study the F + CD3CN → DF + CD2CN reaction in CD3CN solvent (recently reported in Dunning et al. [Science 347(6221), 530 (2015)]). This approach allows us to build a reactive potential energy surface whose balanced accuracy and efficiency considerably surpass what we could achieve otherwise. We ran molecular dynamics simulations to examine a range of observables which follow in the wake of the reactive event: energy deposition in the nascent reaction products, vibrational relaxation rates of excited DF in CD3CN solvent, equilibrium power spectra of DF in CD3CN, and time dependent spectral shifts associated with relaxation of the nascent DF. Many of our results are in good agreement with time-resolved experimental observations, providing evidence for the accuracy of our MS-EVB framework in treating both the solute and solute/solvent interactions. The simulations provide additional insight into the dynamics at sub-picosecond time scales that are difficult to resolve experimentally. In particular, the simulations show that (immediately following deuterium abstraction) the nascent DF finds itself in a non-equilibrium regime in two different respects: (1) it is highly vibrationally excited, with ˜23 kcal mol-1 localized in the stretch and (2) its post-reaction solvation environment, in which it is not yet hydrogen-bonded to CD3CN solvent molecules, is intermediate between the non-interacting gas-phase limit and the solution-phase equilibrium limit. Vibrational relaxation of the nascent DF results in a spectral blue shift, while relaxation of the post-reaction solvation environment results in a red shift. These two competing effects mean that the post-reaction relaxation profile is distinct from what is observed when Franck-Condon vibrational excitation of DF occurs within a microsolvation environment initially at equilibrium. Our conclusions, along with the theoretical and parallel software framework presented in this paper, should be more broadly applicable to a range of complex reactive systems.

Experimental observations of the hydrodynamic behavior of solvent systems in high-speed counter-current chromatography. I. Hydrodynamic distribution of two solvent phases in a helical column subjected to two types of synchronous planetary motion.

PubMed

Ito, Y

1984-10-05

Hydrodynamic distribution of two-phase solvent systems in a rotating helical column subjected to centrifugal fields produced by two different types of synchronous planetary motion has been studied by the use of the combined horizontal flow-through coil planet centrifuge. With continuous elution of the mobile phase, the simpler type of motion resulted in low retention of the stationary phase in the column whereas a more complex motion, which produces a quasi-radial centrifugal field varying in both intensity and direction, yielded high stationary phase retention for commonly used solvent systems having a wide range of hydrophobicity. These solvent systems display highly complex modes of hydrodynamic interaction in the coil according to their particular physical properties.

Determination of emamectin benzoate in medicated fish feed.

PubMed

Farer, L J; Hayes, J; Rosen, J; Knight, P

1999-01-01

A method was developed to quantitate emamectin benzoate in fish feed at levels between 5 and 15 ppm. The active ingredient is extracted from 20 g medicated feed into aqueous-methanolic solvent by overnight shaking. A solid-phase extraction procedure using a 2 g C18 cartridge is then used to concentrate the active residue and remove interfering matrix components. The extracted drug and internal standard are eluted from the cartridge, evaporated to dryness, and reconstituted in methanol. A control feed sample and fortified control working standard are simultaneously prepared. Remaining interferences and sample analysis are further separated on a gradient liquid chromatographic system. Recovery of emamectin benzoate from fortified feeds ranged from 97 to 100%, with a coefficient of variation (CV) of 1.2%. Determination of emamectin benzoate in medicated feeds resulted in CVs ranging from 2.3 to 4.2% and recoveries of 88 to 98% of label claim.

First-Principles and Thermodynamic Simulation of Elastic Stress Effect on Energy of Hydrogen Dissolution in Alpha Iron

NASA Astrophysics Data System (ADS)

Rakitin, M. S.; Mirzoev, A. A.; Mirzaev, D. A.

2018-04-01

Mobile hydrogen, when dissolving in metals, redistributes due to the density gradients and elastic stresses, and enables destruction processes or phase transformations in local volumes of a solvent metal. It is rather important in solid state physics to investigate these interactions. The first-principle calculations performed in terms of the density functional theory, are used for thermodynamic simulation of the elastic stress effect on the energy of hydrogen dissolution in α-Fe crystal lattice. The paper presents investigations of the total energy of Fe-H system depending on the lattice parameter. As a result, the relation is obtained between the hydrogen dissolution energy and stress. A good agreement is shown between the existing data and simulation results. The extended equation is suggested for the chemical potential of hydrogen atom in iron within the local stress field. Two parameters affecting the hydrogen distribution are compared, namely local stress and phase transformations.

[Determination of arbutin in apple juice concentrate by ultra performance liquid chromatography with electrospray ionization tandem mass spectrometry].

PubMed

Kong, Xianghong; He, Qiang; Yue, Aishan; Wu, Shuangmin; Li, Jianhua

2010-06-01

An ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/ MS) method was developed for the determination of arbutin in apple juice concentrate. Samples were diluted with water, then cleaned-up with a PS-DVB column. Quantitation was carried out using an external standard method. UPLC was performed on an Eclipse Plus C, column (100 mm x 2.1 mm, 1.8 microm) using a gradient solvent system (methanol-water). MS/MS was performed with multiple reaction monitoring (MRM) mode. The detection limit of arbutin was 0.02 mg/L. The method showed good linear relationship at the range of 0.04-2.0 mg/L. The recoveries ranged from 75.2% to 102.7% with relative standard deviations (RSDs) less than 8.9%. The method is simple, fast and sensitive. It's suitable for quantitative and qualitative analysis of arbutin in apple juice concentrate.

Controlled Expansion of Supercritical Solution: A Robust Method to Produce Pure Drug Nanoparticles With Narrow Size-Distribution.

PubMed

Pessi, Jenni; Lassila, Ilkka; Meriläinen, Antti; Räikkönen, Heikki; Hæggström, Edward; Yliruusi, Jouko

2016-08-01

We introduce a robust, stable, and reproducible method to produce nanoparticles based on expansion of supercritical solutions using carbon dioxide as a solvent. The method, controlled expansion of supercritical solution (CESS), uses controlled mass transfer, flow, pressure reduction, and particle collection in dry ice. CESS offers control over the crystallization process as the pressure in the system is reduced according to a specific profile. Particle formation takes place before the exit nozzle, and condensation is the main mechanism for postnucleation particle growth. A 2-step gradient pressure reduction is used to prevent Mach disk formation and particle growth by coagulation. Controlled particle growth keeps the production process stable. With CESS, we produced piroxicam nanoparticles, 60 mg/h, featuring narrow size distribution (176 ± 53 nm). Copyright © 2016 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.

Organic Solvent Effects in Biomass Conversion Reactions.

PubMed

Shuai, Li; Luterbacher, Jeremy

2016-01-01

Transforming lignocellulosic biomass into fuels and chemicals has been intensely studied in recent years. A large amount of work has been dedicated to finding suitable solvent systems, which can improve the transformation of biomass into value-added chemicals. These efforts have been undertaken based on numerous research results that have shown that organic solvents can improve both conversion and selectivity of biomass to platform molecules. We present an overview of these organic solvent effects, which are harnessed in biomass conversion processes, including conversion of biomass to sugars, conversion of sugars to furanic compounds, and production of lignin monomers. A special emphasis is placed on comparing the solvent effects on conversion and product selectivity in water with those in organic solvents while discussing the origins of the differences that arise. We have categorized results as benefiting from two major types of effects: solvent effects on solubility of biomass components including cellulose and lignin and solvent effects on chemical thermodynamics including those affecting reactants, intermediates, products, and/or catalysts. Finally, the challenges of using organic solvents in industrial processes are discussed from the perspective of solvent cost, solvent stability, and solvent safety. We suggest that a holistic view of solvent effects, the mechanistic elucidation of these effects, and the careful consideration of the challenges associated with solvent use could assist researchers in choosing and designing improved solvent systems for targeted biomass conversion processes. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The origin of consistent protein structure refinement from structural averaging.

PubMed

Park, Hahnbeom; DiMaio, Frank; Baker, David

2015-06-02

Recent studies have shown that explicit solvent molecular dynamics (MD) simulation followed by structural averaging can consistently improve protein structure models. We find that improvement upon averaging is not limited to explicit water MD simulation, as consistent improvements are also observed for more efficient implicit solvent MD or Monte Carlo minimization simulations. To determine the origin of these improvements, we examine the changes in model accuracy brought about by averaging at the individual residue level. We find that the improvement in model quality from averaging results from the superposition of two effects: a dampening of deviations from the correct structure in the least well modeled regions, and a reinforcement of consistent movements towards the correct structure in better modeled regions. These observations are consistent with an energy landscape model in which the magnitude of the energy gradient toward the native structure decreases with increasing distance from the native state. Copyright © 2015 Elsevier Ltd. All rights reserved.

Solvent Reaction Field Potential inside an Uncharged Globular Protein: A Bridge between Implicit and Explicit Solvent Models?

PubMed Central

Baker, Nathan A.; McCammon, J. Andrew

2008-01-01

The solvent reaction field potential of an uncharged protein immersed in Simple Point Charge/Extended (SPC/E) explicit solvent was computed over a series of molecular dynamics trajectories, intotal 1560 ns of simulation time. A finite, positive potential of 13 to 24 kbTec−1 (where T = 300K), dependent on the geometry of the solvent-accessible surface, was observed inside the biomolecule. The primary contribution to this potential arose from a layer of positive charge density 1.0 Å from the solute surface, on average 0.008 ec/Å3, which we found to be the product of a highly ordered first solvation shell. Significant second solvation shell effects, including additional layers of charge density and a slight decrease in the short-range solvent-solvent interaction strength, were also observed. The impact of these findings on implicit solvent models was assessed by running similar explicit-solvent simulations on the fully charged protein system. When the energy due to the solvent reaction field in the uncharged system is accounted for, correlation between per-atom electrostatic energies for the explicit solvent model and a simple implicit (Poisson) calculation is 0.97, and correlation between per-atom energies for the explicit solvent model and a previously published, optimized Poisson model is 0.99. PMID:17949217

Solvent reaction field potential inside an uncharged globular protein: A bridge between implicit and explicit solvent models?

NASA Astrophysics Data System (ADS)

Cerutti, David S.; Baker, Nathan A.; McCammon, J. Andrew

2007-10-01

The solvent reaction field potential of an uncharged protein immersed in simple point charge/extended explicit solvent was computed over a series of molecular dynamics trajectories, in total 1560ns of simulation time. A finite, positive potential of 13-24 kbTec-1 (where T =300K), dependent on the geometry of the solvent-accessible surface, was observed inside the biomolecule. The primary contribution to this potential arose from a layer of positive charge density 1.0Å from the solute surface, on average 0.008ec/Å3, which we found to be the product of a highly ordered first solvation shell. Significant second solvation shell effects, including additional layers of charge density and a slight decrease in the short-range solvent-solvent interaction strength, were also observed. The impact of these findings on implicit solvent models was assessed by running similar explicit solvent simulations on the fully charged protein system. When the energy due to the solvent reaction field in the uncharged system is accounted for, correlation between per-atom electrostatic energies for the explicit solvent model and a simple implicit (Poisson) calculation is 0.97, and correlation between per-atom energies for the explicit solvent model and a previously published, optimized Poisson model is 0.99.

Development of a Supported Emulsion Liquid Membrane System for Propionic Acid Separation in a Microgravity Environment

NASA Technical Reports Server (NTRS)

Li, Jin; Hu, Shih-Yao B.; Wiencek, John M.

2001-01-01

Perstractive fermentation is a good way to increase the productivity of bioreactors. Using Propionibacteria as the model system, the feasibility of using supported emulsion liquid membrane (SELM) for perstractive fermentation is assessed in this study. Five industrial solvents were considered as the solvent for preparing the SELM. The more polar a solvent is, the higher the partition coefficient. However, toxicity of a solvent also increases with its polarity. CO-1055 (industrial decanol/octanol blend) has the highest partition coefficient toward propionic acid among the solvents that has no molecular toxicity toward Propionibacteria. A preliminary extraction study was conducted using tetradecane as solvent in a hydrophobic hollow fiber contactor. The result confirmed that SELM eliminates the equilibrium limitation of conventional liquid-liquid extraction, and allows the use of a non-toxic solvent with low partition coefficient.

Microwave-assisted extraction with water for fast extraction and simultaneous RP-HPLC determination of phenolic acids in radix Salviae Miltiorrhizae.

PubMed

Fang, Xinsheng; Wang, Jianhua; Zhou, Hongying; Jiang, Xingkai; Zhu, Lixiang; Gao, Xin

2009-07-01

An optimized microwave-assisted extraction method using water (MAE-W) as the extractant and an efficient HPLC analysis method were first developed for the fast extraction and simultaneous determination of D(+)-(3,4-dihydroxyphenyl) lactic acid (Dla), salvianolic acid B (SaB), and lithospermic acid (La) in radix Salviae Miltiorrhizae. The key parameters of MAE-W were optimized. It was found that the degradation of SaB was inhibited when using the optimized MAE-W and the stable content of Dla, La, and SaB in danshen was obtained. Furthermore, compared to the conventional extraction methods, the proposed MAE-W is a more rapid method with higher yield and lower solvent consumption with a reproducibility (RSD <6%). In addition, using water as extractant is safe and helpful for environment protection, which could be referred to as green extraction. The separation and quantitative determination of the three compounds was carried out by a developed reverse-phase high-performance liquid chromatographic (RP-HPLC) method with UV detection. Highly efficient separation was obtained using gradient solvent system. The optimized HPLC analysis method was validated to have specificity, linearity, precision, and accuracy. The results indicated that MAE-W followed by HPLC-UV determination is an appropriate alternative to previously proposed method for quality control of radix Salviae Miltiorrhizae.

Ionic Liquid-Liquid Chromatography: A New General Purpose Separation Methodology.

PubMed

Brown, Leslie; Earle, Martyn J; Gîlea, Manuela A; Plechkova, Natalia V; Seddon, Kenneth R

2017-08-10

Ionic liquids can form biphasic solvent systems with many organic solvents and water, and these solvent systems can be used in liquid-liquid separations and countercurrent chromatography. The wide range of ionic liquids that can by synthesised, with specifically tailored properties, represents a new philosophy for the separation of organic, inorganic and bio-based materials. A customised countercurrent chromatograph has been designed and constructed specifically to allow the more viscous character of ionic liquid-based solvent systems to be used in a wide variety of separations (including transition metal salts, arenes, alkenes, alkanes, bio-oils and sugars).

Denaturing Gradient Gel Electrophoresis-Polymerase Chain Reaction Comparison of Chitosan Effects on Anaerobic Cultures of Broiler Cecal Bacteria and Salmonella Typhimurium.

PubMed

Hume, Michael; Sohail, Muhammad Umar

2018-04-01

Enteropathogen colonization and product contamination are major poultry industry problems. The emergence of antibiotic resistance, and associated risks to human health, is limiting the use of antibiotics as first-line defense against enteropathogens in poultry. The chitin derivative, chitosan, has drawn substantial attention for its bactericidal properties. Different molecular weight (MW) chitosans can have varied effects against different bacteria in monoculture. In the current study, cecal contents from each of three market-age broilers and Salmonella Typhimurium, as indicator enteropathogen, were exposed to in vitro anaerobic culture to three chitosan preparations (0.08%, wt/vol), low (LMW), medium (MMW), and coarse (CMW). Effects of chitosan and the carrier solvent acetic acid, on cecal bacteria and Salmonella, were examined by denaturing gradient gel electrophoresis (DGGE) and Salmonella enumeration. Bacterial profiles for the three cecal contents were shown by DGGE to be very different. Each of the three cecal contents grown in the presence of 0.08% acetic acid was very different from the same contents grown without the chitosan solvent. Culturing cecal contents in the presence of chitosan altered the bacterial DGGE profiles from the control and acetic acid-only cultures. The DGGE chitosan-treated profiles for all three cecal sources were identical to each other regardless of the MW chitosan in the culture medium. Compared with Salmonella in monoculture, Salmonella decreased (p < 0.05) by about 1.5 log CFU/mL when grown in mixed culture with cecal contents. Salmonella monocultures in the presence of 0.08% of the chitosan solvent acetic acid decreased (p < 0.05) counts by almost 3.5 log CFU/mL. Combining acetic acid and cecal contents reduced (p < 0.05) Salmonella by 7 log CFU/mL. Adding the chitosan preparations to the mixtures reduced (p < 0.05) Salmonella by 8 log CFU/mL.

Determination of reversed-phase high performance liquid chromatography based octanol-water partition coefficients for neutral and ionizable compounds: Methodology evaluation.

PubMed

Liang, Chao; Qiao, Jun-Qin; Lian, Hong-Zhen

2017-12-15

Reversed-phase liquid chromatography (RPLC) based octanol-water partition coefficient (logP) or distribution coefficient (logD) determination methods were revisited and assessed comprehensively. Classic isocratic and some gradient RPLC methods were conducted and evaluated for neutral, weak acid and basic compounds. Different lipophilicity indexes in logP or logD determination were discussed in detail, including the retention factor logk w corresponding to neat water as mobile phase extrapolated via linear solvent strength (LSS) model from isocratic runs and calculated with software from gradient runs, the chromatographic hydrophobicity index (CHI), apparent gradient capacity factor (k g ') and gradient retention time (t g ). Among the lipophilicity indexes discussed, logk w from whether isocratic or gradient elution methods best correlated with logP or logD. Therefore logk w is recommended as the preferred lipophilicity index for logP or logD determination. logk w easily calculated from methanol gradient runs might be the main candidate to replace logk w calculated from classic isocratic run as the ideal lipophilicity index. These revisited RPLC methods were not applicable for strongly ionized compounds that are hardly ion-suppressed. A previously reported imperfect ion-pair RPLC method was attempted and further explored for studying distribution coefficients (logD) of sulfonic acids that totally ionized in the mobile phase. Notably, experimental logD values of sulfonic acids were given for the first time. The IP-RPLC method provided a distinct way to explore logD values of ionized compounds. Copyright © 2017 Elsevier B.V. All rights reserved.

Assessing the Impact of Chlorinated-Solvent Sites on Metropolitan Groundwater Resources

PubMed Central

Brusseau, Mark L.; Narter, Matthew

2014-01-01

Chlorinated-solvent compounds are among the most common groundwater contaminants in the U.S.A. The majority of the many sites contaminated by chlorinated-solvent compounds are located in metropolitan areas, and most such areas have one or more chlorinated-solvent contaminated sites. Thus, contamination of groundwater by chlorinated-solvent compounds may pose a potential risk to the sustainability of potable water supplies for many metropolitan areas. The impact of chlorinated-solvent sites on metropolitan water resources was assessed for Tucson, AZ, by comparing the aggregate volume of extracted groundwater for all pump-and-treat systems associated with contaminated sites in the region to the total regional groundwater withdrawal. The analysis revealed that the aggregate volume of groundwater withdrawn for the pump-and-treat systems operating in Tucson, all of which are located at chlorinated-solvent contaminated sites, was 20% of the total groundwater withdrawal in the city for the study period. The treated groundwater was used primarily for direct delivery to local water supply systems or for reinjection as part of the pump-and-treat system. The volume of the treated groundwater used for potable water represented approximately 13% of the total potable water supply sourced from groundwater, and approximately 6% of the total potable water supply. This case study illustrates the significant impact chlorinated-solvent contaminated sites can have on groundwater resources and regional potable-water supplies. PMID:24116872

A General Strategy for Nanohybrids Synthesis via Coupled Competitive Reactions Controlled in a Hybrid Process

PubMed Central

Wang, Rongming; Yang, Wantai; Song, Yuanjun; Shen, Xiaomiao; Wang, Junmei; Zhong, Xiaodi; Li, Shuai; Song, Yujun

2015-01-01

A new methodology based on core alloying and shell gradient-doping are developed for the synthesis of nanohybrids, realized by coupled competitive reactions, or sequenced reducing-nucleation and co-precipitation reaction of mixed metal salts in a microfluidic and batch-cooling process. The latent time of nucleation and the growth of nanohybrids can be well controlled due to the formation of controllable intermediates in the coupled competitive reactions. Thus, spatiotemporal-resolved synthesis can be realized by the hybrid process, which enables us to investigate nanohybrid formation at each stage through their solution color changes and TEM images. By adjusting the bi-channel solvents and kinetic parameters of each stage, the primary components of alloyed cores and the second components of transition metal doping ZnO or Al2O3 as surface coatings can be successively formed. The core alloying and shell gradient-doping strategy can efficiently eliminate the crystal lattice mismatch in different components. Consequently, varieties of gradient core-shell nanohybrids can be synthesized using CoM, FeM, AuM, AgM (M = Zn or Al) alloys as cores and transition metal gradient-doping ZnO or Al2O3 as shells, endowing these nanohybrids with unique magnetic and optical properties (e.g., high temperature ferromagnetic property and enhanced blue emission). PMID:25818342

External-Field-Induced Gradient Wetting for Controllable Liquid Transport: From Movement on the Surface to Penetration into the Surface.

PubMed

Li, Yan; He, Linlin; Zhang, Xiaofang; Zhang, Na; Tian, Dongliang

2017-12-01

External-field-responsive liquid transport has received extensive research interest owing to its important applications in microfluidic devices, biological medical, liquid printing, separation, and so forth. To realize different levels of liquid transport on surfaces, the balance of the dynamic competing processes of gradient wetting and dewetting should be controlled to achieve good directionality, confined range, and selectivity of liquid wetting. Here, the recent progress in external-field-induced gradient wetting is summarized for controllable liquid transport from movement on the surface to penetration into the surface, particularly for liquid motion on, patterned wetting into, and permeation through films on superwetting surfaces with external field cooperation (e.g., light, electric fields, magnetic fields, temperature, pH, gas, solvent, and their combinations). The selected topics of external-field-induced liquid transport on the different levels of surfaces include directional liquid motion on the surface based on the wettability gradient under an external field, partial entry of a liquid into the surface to achieve patterned surface wettability for printing, and liquid-selective permeation of the film for separation. The future prospects of external-field-responsive liquid transport are also discussed. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Initial solubility & density evaluation of Non-Aqueous system of amino acid salts for CO2 capture: potassium prolinate blended with ethanol and ethylene glycol

NASA Astrophysics Data System (ADS)

Murshid, Ghulam; Garg, Sahil

2018-05-01

Amine scrubbing is the state of the art technology for CO2 capture, and solvent selection can significantly reduce the capital and energy cost of the process. Higher energy requirement for aqueous amine based CO2 removal process is still a most important downside preventive its industrial deployment. Therefore, in this study, novel non-aqueous based amino acid salt system consisting of potassium prolinate, ethanol and ethylene glycol has been studied. This work presents initial CO2 solubility study and important physical properties i.e. density of the studied solvent system. Previous work showed that non-aqueous system of potassium prolinate and ethanol has good absorption rates and requires lower energy for solvent regeneration. However, during regeneration, solvent loss issues were found due to lower boiling point of the ethanol. Therefore, ethylene glycol was added into current studied system for enhancing the overall boiling point of the system. The good initial CO2 solubility and low density of studied solvent system offers several advantages as compared to conventional amine solutions.

Improved Supercritical-Solvent Extraction of Coal

NASA Technical Reports Server (NTRS)

Compton, L.

1982-01-01

Raw coal upgraded by supercritical-solvent extraction system that uses two materials instead of one. System achieved extraction yields of 20 to 49 weight percent. Single-solvent yields are about 25 weight percent. Experimental results show extraction yields may be timedependent. Observed decreases in weight of coal agreed well with increases in ash content of residue.

GREEN CATALYZED OXIDATION OF HYDROCARBONS IN ALTERNATIVE SOLVENT SYSTEMS GENERATED BY PARIS II DECHEMA; GREEN SOLVENTS FOR CATALYSIS - ENVIRONMENTALLY BENIGN REACTION MEDIA

EPA Science Inventory

Green catalyzed oxidation of hydrocarbons in alternative solvent systems generated by PARIS II
Thomas M. Becker, Michael A. Gonzalez, Paul F. Harten; Sustainable Technology Division, Office of Research and Development; United States Environmental Protection Agency, 26 West Mar...

Method of removing contaminants from plastic resins

DOEpatents

Bohnert, George W.; Hand, Thomas E.; DeLaurentiis, Gary M.

2008-11-18

A method for removing contaminants from synthetic resin material containers using a first organic solvent system and a second carbon dioxide system. The organic solvent is utilized for removing the contaminants from the synthetic resin material and the carbon dioxide is used to separate any residual organic solvent from the synthetic resin material.

Method of removing contaminants from plastic resins

DOEpatents

Bohnert, George W [Harrisonville, MO; Hand, Thomas E [Lee's Summit, MO; Delaurentiis, Gary M [Jamestown, CA

2007-08-07

A method for removing contaminants from synthetic resin material containers using a first organic solvent system and a second carbon dioxide system. The organic solvent is utilized for removing the contaminants from the synthetic resin material and the carbon dioxide is used to separate any residual organic solvent from the synthetic resin material.

Method for removing contaminants from plastic resin

DOEpatents

Bohnert, George W.; Hand, Thomas E.; DeLaurentiis, Gary M.

2008-12-30

A method for removing contaminants from synthetic resin material containers using a first organic solvent system and a second carbon dioxide system. The organic solvent is utilized for removing the contaminants from the synthetic resin material and the carbon dioxide is used to separate any residual organic solvent from the synthetic resin material.

Separation of polysaccharides from rice husk and wheat bran using solvent system consisting of BMIMOAc and DMI.

PubMed

Hou, Qidong; Li, Weizun; Ju, Meiting; Liu, Le; Chen, Yu; Yang, Qian; Wang, Jingyu

2015-11-20

A solvent system consisting of 1,3-dimethyl-2-imidazolidinone (DMI), and ionic liquid 1-butyl-3-methylimidazolium acetate (BMIMOAc) was used to separate polysaccharides from rice husk and wheat bran. The effects of the DMI/BMIMOAc ratios, temperature, and time on the dissolution of rice husk and wheat bran were investigated, and the influence of anti-solvents on the regeneration of polysaccharides-rich material was evaluated. We found that the solvent system is more powerful to dissolve rice husk and wheat bran than pure BMIMOAc, and that polysaccharides-rich material can be effectively separated from the biomass solution. The polysaccharides content of regenerated material from wheat bran can reach as high as 94.4% when ethanol was used as anti-solvents. Under optimized conditions, the extraction rate of polysaccharides for wheat bran can reach as high as 71.8% at merely 50°C. The recycled solvent system exhibited constant ability to separate polysaccharides from rice husk and wheat bran. Copyright © 2015 Elsevier Ltd. All rights reserved.

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

NASA Astrophysics Data System (ADS)

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

2016-12-01

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

The Search for Nonflammable Solvent Alternatives for Cleaning Aerospace Oxygen Systems

NASA Technical Reports Server (NTRS)

Mitchell, Mark A.; Lowrey, Nikki

2012-01-01

To obtain a high degree of cleanliness without risk of corrosion or hazardous reactivity, hydrochlorofluorocarbon (HCFC)-225 is used for cleaning and cleanliness verification of oxygen system components used on NASA fs bipropellant launch vehicles, associated test stands and support equipment. HCFC-225 is a Class II Ozone Depleting Substance (ODS ]II) that was introduced to replace chlorofluorocarbon (CFC)-113, a Class I ODS solvent that is now banned. To meet environmental regulations to eliminate the use of ozone depleting substances, a replacement solvent is required for HCFC ]225 that is effective at removing oils, greases, and particulate from large oxygen system components, is compatible with materials used in the construction of these systems, and is nonflammable and non ]reactive in enriched oxygen environments. A solvent replacement is also required for aviator fs breathing oxygen systems and other related equipment currently cleaned and verified with HCFC ]225 and stockpiled CFC -113. Requirements and challenges in the search for nonflammable replacement solvents are discussed.

ORGANIC-HIGH IONIC STRENGTH AQUEOUS SOLVENT SYSTEMS FOR SPIRAL COUNTER-CURRENT CHROMATOGRAPHY: GRAPHIC OPTIMIZATION OF PARTITION COEFFICIENT

PubMed Central

Zeng, Yun; Liu, Gang; Ma, Ying; Chen, Xiaoyuan; Ito, Yoichiro

2012-01-01

A new series of organic-high ionic strength aqueous two-phase solvents systems was designed for separation of highly polar compounds by spiral high-speed counter-current chromatography. A total of 21 solvent systems composed of 1-butanol-ethanol-saturated ammonium sulfate-water at various volume ratios are arranged according to an increasing order of polarity. Selection of the two-phase solvent system for a single compound or a multiple sample mixture can be achieved by two steps of partition coefficient measurements using a graphic method. The capability of the method is demonstrated by optimization of partition coefficient for seven highly polar samples including tartrazine (K=0.77), tryptophan (K=1.00), methyl green (K= 0.93), tyrosine (0.81), metanephrine (K=0.89), tyramine (K=0.98), and normetanephrine (K=0.96). Three sulfonic acid components in D&C Green No. 8 were successfully separated by HSCCC using the graphic selection of the two-phase solvent system. PMID:23467197

SOLVENT EXTRACTION PROCESS FOR THE SEPARATION OF URANIUM AND THORIUM FROM PROTACTINIUM AND FISSION PRODUCTS

DOEpatents

Rainey, R.H.; Moore, J.G.

1962-08-14

A liquid-liquid extraction process was developed for recovering thorium and uranium values from a neutron irradiated thorium composition. They are separated from a solvent extraction system comprising a first end extraction stage for introducing an aqueous feed containing thorium and uranium into the system consisting of a plurality of intermediate extractiorr stages and a second end extractron stage for introducing an aqueous immiscible selective organic solvent for thorium and uranium in countercurrent contact therein with the aqueous feed. A nitrate iondeficient aqueous feed solution containing thorium and uranium was introduced into the first end extraction stage in countercurrent contact with the organic solvent entering the system from the second end extraction stage while intro ducing an aqueous solution of salting nitric acid into any one of the intermediate extraction stages of the system. The resultant thorium and uranium-laden organic solvent was removed at a point preceding the first end extraction stage of the system. (AEC)

STABILITY OF A CYLINDRICAL SOLUTE-SOLVENT INTERFACE: EFFECT OF GEOMETRY, ELECTROSTATICS, AND HYDRODYNAMICS.

PubMed

Li, B O; Sun, Hui; Zhou, Shenggao

The solute-solvent interface that separates biological molecules from their surrounding aqueous solvent characterizes the conformation and dynamics of such molecules. In this work, we construct a solvent fluid dielectric boundary model for the solvation of charged molecules and apply it to study the stability of a model cylindrical solute-solvent interface. The motion of the solute-solvent interface is defined to be the same as that of solvent fluid at the interface. The solvent fluid is assumed to be incompressible and is described by the Stokes equation. The solute is modeled simply by the ideal-gas law. All the viscous force, hydrostatic pressure, solute-solvent van der Waals interaction, surface tension, and electrostatic force are balanced at the solute-solvent interface. We model the electrostatics by Poisson's equation in which the solute-solvent interface is treated as a dielectric boundary that separates the low-dielectric solute from the high-dielectric solvent. For a cylindrical geometry, we find multiple cylindrically shaped equilibrium interfaces that describe polymodal (e.g., dry and wet) states of hydration of an underlying molecular system. These steady-state solutions exhibit bifurcation behavior with respect to the charge density. For their linearized systems, we use the projection method to solve the fluid equation and find the dispersion relation. Our asymptotic analysis shows that, for large wavenumbers, the decay rate is proportional to wavenumber with the proportionality half of the ratio of surface tension to solvent viscosity, indicating that the solvent viscosity does affect the stability of a solute-solvent interface. Consequences of our analysis in the context of biomolecular interactions are discussed.

System and method for treatment of a flue gas

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

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

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

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

PubMed

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

2004-03-01

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

Structure and properties of polycaprolactone/chitosan nonwovens tailored by solvent systems.

PubMed

Urbanek, Olga; Sajkiewicz, Paweł; Pierini, Filippo; Czerkies, Maciej; Kołbuk, Dorota

2017-02-03

Electrospinning of chitosan blends is a reasonable idea to prepare fibre mats for biomedical applications. Synthetic and natural components provide, for example, appropriate mechanical strength and biocompatibility, respectively. However, solvent characteristics and the polyelectrolyte nature of chitosan influence the spinnability of these blends. In order to compare the effect of solvent on polycaprolactone/chitosan fibres, two types of the most commonly used solvent systems were chosen, namely 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) and acetic acid (AA)/formic acid (FA). Results obtained by various experimental methods clearly indicated the effect of the solvent system on the structure and properties of electrospun polycaprolactone/chitosan fibres. Viscosity measurements confirmed different polymer-solvent interactions. Various molecular interactions resulting in different macromolecular conformations of chitosan influenced its spinnability and properties. HFIP enabled fibres to be obtained whose average diameter was less than 250 nm while maintaining the brittle and hydrophilic character of the nonwoven, typical for the chitosan component. Spectroscopy studies revealed the formation of chitosan salts in the case of the AA/FA solvent system. Chitosan salts visibly influenced the structure and properties of the prepared fibre mats. The use of AA/FA caused a reduction of Young's modulus and wettability of the proposed blends. It was confirmed that wettability, mechanical properties and the antibacterial effect of polycaprolactone/chitosan fibres may be tailored by selecting an appropriate solvent system. The MTT cell proliferation assay revealed an increase of cytotoxicity to mouse fibroblasts in the case of 25% w/w of chitosan in electrospun nonwovens.

Bench-Scale Silicone Process for Low-Cost CO{sub 2} Capture

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

Wood, Benjamin; Genovese, Sarah; Perry, Robert

2013-12-31

A bench-scale system was designed and built to test an aminosilicone-based solvent. A model was built of the bench-scale system and this model was scaled up to model the performance of a carbon capture unit, using aminosilicones, for CO{sub 2} capture and sequestration (CCS) for a pulverized coal (PC) boiler at 550 MW. System and economic analysis for the carbon capture unit demonstrates that the aminosilicone solvent has significant advantages relative to a monoethanol amine (MEA)-based system. The CCS energy penalty for MEA is 35.9% and the energy penalty for aminosilicone solvent is 30.4% using a steam temperature of 395more » °C (743 °F). If the steam temperature is lowered to 204 °C (400 °F), the energy penalty for the aminosilicone solvent is reduced to 29%. The increase in cost of electricity (COE) over the non-capture case for MEA is ~109% and increase in COE for aminosilicone solvent is ~98 to 103% depending on the solvent cost at a steam temperature of 395 °C (743 °F). If the steam temperature is lowered to 204 °C (400 °F), the increase in COE for the aminosilicone solvent is reduced to ~95-100%.« less

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

PubMed Central

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

2017-01-01

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

Theoretical study of solvent effects on the electronic coupling matrix elements in rigidly linked donor-acceptor systems

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

Cave, R.J.; Newton, M.D.; Kumar, K.

1995-12-07

The recently developed generalized Mulliken-Hush approach for the calculation of the electronic coupling matrix element for electron-transfer processes is applied to two rigidly linked donor-bridge-acceptor systems having dimethoxyanthracene as the donor and a dicarbomethoxycyclobutene unit as the acceptor. The dependence of the electronic coupling matrix element as a function of bridge type is examined with and without solvent molecules present. For clamp-shaped bridge structures solvent can have a dramatic effect on the electronic coupling matrix element. The behavior with variation of solvent is in good agreement with that observed experimentally for these systems. 23 refs., 2 tabs.

Binary breath figures for straightforward and controllable self-assembly of microspherical caps.

PubMed

Gong, Jianliang; Xu, Bingang; Tao, Xiaoming; Li, Lei

2016-05-11

The intense interest surrounding asymmetrical microparticles originates from their unique anisotropic properties and promising applications. In this work, direct self-assembly of polymeric microspherical caps without the assistance of any additives has been achieved by using low-surface-tension methanol (MeOH) and high-surface-tension water as binary breath figures (BFs). With the evaporation of polystyrene (PS) solution containing low-boiling-point solvent in the binary vapors, the formed MeOH BFs could quickly diffuse into solution, while water BFs tended to remain at the solution surface. This led to the formation of a gradient nonsolvent layer at the vapor/solution interface, which induced the formation of nuclei and guided further asymmetrical growth of polymer particles. After the spontaneous removal of MeOH, water and residual solvent by evaporation, polymeric microspherical caps were left on the substrate. Through controlling the proportion of water introduced by adjusting the ratios of MeOH and water, polymeric microspherical caps with a range of controllable shapes (divided at different positions of a sphere) were successfully obtained. The formation mechanism was explained based on the difference of vapor pressure, surface tension and miscibility between the employed solvents and nonsolvents. A solvent possessing a high vapor pressure, low surface tension and good miscibility with MeOH contributed to the formation of microspherical caps. This flexible, green and straightforward technique is a nondestructive strategy, and avoids complicated work on design, preparation and removal of hard templates and additives.

Gradient design for liquid chromatography using multi-scale optimization.

PubMed

López-Ureña, S; Torres-Lapasió, J R; Donat, R; García-Alvarez-Coque, M C

2018-01-26

In reversed phase-liquid chromatography, the usual solution to the "general elution problem" is the application of gradient elution with programmed changes of organic solvent (or other properties). A correct quantification of chromatographic peaks in liquid chromatography requires well resolved signals in a proper analysis time. When the complexity of the sample is high, the gradient program should be accommodated to the local resolution needs of each analyte. This makes the optimization of such situations rather troublesome, since enhancing the resolution for a given analyte may imply a collateral worsening of the resolution of other analytes. The aim of this work is to design multi-linear gradients that maximize the resolution, while fulfilling some restrictions: all peaks should be eluted before a given maximal time, the gradient should be flat or increasing, and sudden changes close to eluting peaks are penalized. Consequently, an equilibrated baseline resolution for all compounds is sought. This goal is achieved by splitting the optimization problem in a multi-scale framework. In each scale κ, an optimization problem is solved with N κ  ≈ 2 κ variables that are used to build the gradients. The N κ variables define cubic splines written in terms of a B-spline basis. This allows expressing gradients as polygonals of M points approximating the splines. The cubic splines are built using subdivision schemes, a technique of fast generation of smooth curves, compatible with the multi-scale framework. Owing to the nature of the problem and the presence of multiple local maxima, the algorithm used in the optimization problem of each scale κ should be "global", such as the pattern-search algorithm. The multi-scale optimization approach is successfully applied to find the best multi-linear gradient for resolving a mixture of amino acid derivatives. Copyright © 2017 Elsevier B.V. All rights reserved.

Nonadiabatic dynamics of electron transfer in solution: Explicit and implicit solvent treatments that include multiple relaxation time scales

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

Schwerdtfeger, Christine A.; Soudackov, Alexander V.; Hammes-Schiffer, Sharon, E-mail: shs3@illinois.edu

2014-01-21

The development of efficient theoretical methods for describing electron transfer (ET) reactions in condensed phases is important for a variety of chemical and biological applications. Previously, dynamical dielectric continuum theory was used to derive Langevin equations for a single collective solvent coordinate describing ET in a polar solvent. In this theory, the parameters are directly related to the physical properties of the system and can be determined from experimental data or explicit molecular dynamics simulations. Herein, we combine these Langevin equations with surface hopping nonadiabatic dynamics methods to calculate the rate constants for thermal ET reactions in polar solvents formore » a wide range of electronic couplings and reaction free energies. Comparison of explicit and implicit solvent calculations illustrates that the mapping from explicit to implicit solvent models is valid even for solvents exhibiting complex relaxation behavior with multiple relaxation time scales and a short-time inertial response. The rate constants calculated for implicit solvent models with a single solvent relaxation time scale corresponding to water, acetonitrile, and methanol agree well with analytical theories in the Golden rule and solvent-controlled regimes, as well as in the intermediate regime. The implicit solvent models with two relaxation time scales are in qualitative agreement with the analytical theories but quantitatively overestimate the rate constants compared to these theories. Analysis of these simulations elucidates the importance of multiple relaxation time scales and the inertial component of the solvent response, as well as potential shortcomings of the analytical theories based on single time scale solvent relaxation models. This implicit solvent approach will enable the simulation of a wide range of ET reactions via the stochastic dynamics of a single collective solvent coordinate with parameters that are relevant to experimentally accessible systems.« less

Process for enhancing the value of hydrocabonaceous natural recources

DOEpatents

Bunger, James W.; Cogswell, Donald E.

2005-04-05

A process for upgrading hydrocarbonaceous oil containing heteroatom-containing compounds where the hydrocarbonaceous oil is contacted with a solvent system that is a mixture of a major portion of a polar solvent having a dipole moment greater than about 1 debye and a minor portion of water to selectively separate the constituents of the carbonaceous oil into a heteroatom-depleted raffinate fraction and heteroatom-enriched extract fraction. The polar solvent and the water-in-solvent system are formulated at a ratio where the water is an antisolvent in an amount to inhibit solubility of heteroatom-containing compounds and the polar solvent in the raffinate, and to inhibit solubility of non-heteroatom-containing compounds in the extract. The ratio of the hydrocarbonaceous oil to the solvent system is such that a coefficient of separation is at least 50%. The coefficient of separation is the mole percent of heteroatom-containing compounds from the carbonaceous oil that are recovered in the extract fraction minus the mole percent of non-heteroatom-containing compounds from the carbonaceous oil that are recovered in the extract fraction. The solvent-free extract and the raffinate concentrates may be used directly or processed to make valuable petroleum, chemical or industrial products.

Evaluation of various solvent systems for lipid extraction from wet microalgal biomass and its effects on primary metabolites of lipid-extracted biomass.

PubMed

Ansari, Faiz Ahmad; Gupta, Sanjay Kumar; Shriwastav, Amritanshu; Guldhe, Abhishek; Rawat, Ismail; Bux, Faizal

2017-06-01

Microalgae have tremendous potential to grow rapidly, synthesize, and accumulate lipids, proteins, and carbohydrates. The effects of solvent extraction of lipids on other metabolites such as proteins and carbohydrates in lipid-extracted algal (LEA) biomass are crucial aspects of algal biorefinery approach. An effective and economically feasible algae-based oil industry will depend on the selection of suitable solvent/s for lipid extraction, which has minimal effect on metabolites in lipid-extracted algae. In current study, six solvent systems were employed to extract lipids from dry and wet biomass of Scenedesmus obliquus. To explore the biorefinery concept, dichloromethane/methanol (2:1 v/v) was a suitable solvent for dry biomass; it gave 18.75% lipids (dry cell weight) in whole algal biomass, 32.79% proteins, and 24.73% carbohydrates in LEA biomass. In the case of wet biomass, in order to exploit all three metabolites, isopropanol/hexane (2:1 v/v) is an appropriate solvent system which gave 7.8% lipids (dry cell weight) in whole algal biomass, 20.97% proteins, and 22.87% carbohydrates in LEA biomass. Graphical abstract: Lipid extraction from wet microalgal biomass and biorefianry approach.

The Search for Nonflammable Solvent Alternatives for Cleaning Aerospace Oxygen Systems

NASA Technical Reports Server (NTRS)

Mitchell, Mark; Lowrey, Nikki

2012-01-01

Oxygen systems are susceptible to fires caused by particle and nonvolatile residue (NVR) contaminants, therefore cleaning and verification is essential for system safety. . Cleaning solvents used on oxygen system components must be either nonflammable in pure oxygen or complete removal must be assured for system safety. . CFC -113 was the solvent of choice before 1996 because it was effective, least toxic, compatible with most materials of construction, and non ]reactive with oxygen. When CFC -113 was phased out in 1996, HCFC -225 was selected as an interim replacement for cleaning propulsion oxygen systems at NASA. HCFC-225 production phase-out date is 01/01/2015. HCFC ]225 (AK ]225G) is used extensively at Marshall Space Flight Center and Stennis Space Center for cleaning and NVR verification on large propulsion oxygen systems, and propulsion test stands and ground support equipment. . Many components are too large for ultrasonic agitation - necessary for effective aqueous cleaning and NVR sampling. . Test stand equipment must be cleaned prior to installation of test hardware. Many items must be cleaned by wipe or flush in situ where complete removal of a flammable solvent cannot be assured. The search for a replacement solvent for these applications is ongoing.

Solvent Replacement for Hydrochlorofluorocarbon-225 for Cleaning Oxygen System Components

NASA Technical Reports Server (NTRS)

Mitchell, M. A.; Lowrey, N. M.

2017-01-01

This Technical Memorandum is the result of a 2-year project funded by the Defense Logistics Agency-Aviation, Hazardous Minimization and Green Products Branch, to identify and test two candidate solvents to replace hydrochlorofluorocarbon-225 (HCFC-225) for cleaning oxygen systems. The solvents were also compared to a second solvent composed predominantly of perfluorobutyl iodide (PFBI), which had received limited approval by the United States Air Force (USAF) for hand wipe cleaning of components for aviators’ breathing oxygen systems. The tests performed for this study were based on those reported in AFRL-ML-WP-TR-2003-4040, “The Wipe Solvent Program,” the test program used to qualify Ikon® Solvent P for USAF applications.The study was completed in August 2014, prior to the completion of a more extensive study funded by the NASA Rocket Propulsion Test (RPT) program. The results of the RPT project are reported in NASA/TP-2015-18207, “Replacement of Hydrochlorofluorocarbon–225 Solvent for Cleaning and Verification Sampling of NASA Propulsion Oxygen Systems Hardware, Ground Support Equipment, and Associated Test Systems.” The test methods used in this study for nonvolatile residue (NVR) background, materials compatibility, and cleaning effectiveness were different than those used for the RPT project; a smaller set of materials and contaminants were tested. The tests for this study were complementary to and provided supplementary information for the down-selection process during the course of the test program reported in NASA/TP-2015-218207.

Tailoring magnetic nanoparticle for transformers application.

PubMed

Morais, P C; Silva, A S; Leite, E S; Garg, V K; Oliveira, A C; Viali, W R; Sartoratto, P P C

2010-02-01

In this study photoacoustic spectroscopy was used to investigate the effect of dilution of an oil-based magnetic fluid sample on the magnetic nanoparticle surface-coating. Changes of the photoacoustic signal intensity on the band-L region (640 to 830 nm) upon dilution of the stock magnetic fluid sample were discussed in terms of molecular surface desorption. The model proposed here assumes that the driving force taking the molecules out from the nanoparticle surface into the bulk solvent is the gradient of osmotic pressure. This gradient of osmotic pressure is established between the nanoparticle surface and the bulk suspension. It is further assumed that the photoacoustic signal intensity (area under the photoacoustic spectra) scales linearly with the number of coating molecules (surface grafting) at the nanoparticle surface. This model picture provides a non-linear analytical description for the reduction of the surface grafting coefficient upon dilution, which was successfully-used to curve-fit the photoacoustic experimental data.

Determination of buoyant density and sensitivity to chloroform and freon for the etiological agent of infectious salmonid anaemia

USGS Publications Warehouse

Christie, K.E.; Hjeltnes, B.; Uglenes , I.; Winton, J.R.

1993-01-01

Plasma was collected from Atlantic salmon Salrno salar with acute infectious salmon anaemia (ISA) and used to challenge Atlantic salmon parr by intraperitoneal injection. Treatment of plasma with the lipid solvent, chloroform, showed that the etiological agent of ISA contained essential lipids, probably as a viral envelope. Some infectivity remained following treatment with freon. Injection challenges using fractions from equilibrium density gradient centrifugation of plasma from fish with acute ISA revealed a band of infectivity in the range 1.184 to 1.262 g cm-3. The band was believed to conta~n both complete ISA-virus particles and infectious particles lacking a complete envelope, nucleocapsid or genome. Density gradient centrifugation of infectious plasma for enrichment of the putative ISA virus appeared to offer a suitable method for obtaining virus-specific nucleic acid for use in the construction of cDNA libraries. 

Unwanted signal leakage in excitation sculpting with single axis gradients.

PubMed

Jerschow, A

1999-03-01

Excitation sculpting (T-L. Hwang and A. J. Shaka, J. Magn. Reson. A 112, 275-279 (1995)) used for solvent suppression and selective excitation in NMR bases its success on the ability to remove baseline and phase errors created by the application of selective rf pulses. This is achieved by the application of two pulsed field gradient (PFG) echoes in sequence. It is essential that the two pairs of PFGs select the coherence transfer steps independently of each other, which is conveniently achieved if they are applied along orthogonal spatial axes. Here, the much more common case where both PFG pairs must be applied along a single axis is investigated. This is shown to lead to complications for certain ratios of PFG strengths. The original theory of excitation sculpting is restated in the spherical basis for convenience. Some of the effects can only be explained by invoking the dipolar demagnetizing field. Copyright 1999 Academic Press.

Analysis of low molecular weight acids by monolithic immobilized pH gradient-based capillary isoelectric focusing coupled with mass spectrometry.

PubMed

Wang, Tingting; Fekete, Agnes; Gaspar, Andras; Ma, Junfeng; Liang, Zhen; Yuan, Huiming; Zhang, Lihua; Schmitt-Kopplin, Philippe; Zhang, Yukui

2011-02-01

A novel method for the separation and detection of low molecular weight (LMW) acids was developed using monolithic immobilized pH gradient-based capillary isoelectric focusing coupled with mass spectrometry. Two main parameters, focusing conditions and delivery buffer conditions, which might affect separation efficiency, were optimized with the focusing time of 7 min at 350 V/cm and the delivery buffer of 50% (v/v) acetonitrile in 10 mmol/L ammonium formate (pH 3.0). Under these conditions, the linear correlation between the volume of delivery solvent and the pK(a) of the model components was observed. In addition, the separation mechanism of LMW acids was proposed as well. We suppose that this method may provide a useful tool for the characterization of LMW components (e.g. natural organic matter of different origins). Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Method to produce biomass-derived compounds using a co-solvent system containing gamma-valerolactone

DOEpatents

Dumesic, James A.; Motagamwala, Ali Hussain

2017-06-27

A method to produce an aqueous solution of carbohydrates containing C5- and/or C6-sugar-containing oligomers and/or C5- and/or C6-sugar monomers in which biomass or a biomass-derived reactant is reacted with a solvent system having an organic solvent, and organic co-solvent, and water, in the presence of an acid. The method produces the desired product, while a substantial portion of any lignin present in the reactant appears as a precipitate in the product mixture.

Thermodynamically based solvent design for enzymatic saccharide acylation with hydroxycinnamic acids in non-conventional media.

PubMed

Zeuner, Birgitte; Kontogeorgis, Georgios M; Riisager, Anders; Meyer, Anne S

2012-02-15

Enzyme-catalyzed synthesis has been widely studied with lipases (EC 3.1.1.3), but feruloyl esterases (FAEs; EC 3.1.1.73) may provide advantages such as higher substrate affinity and regioselectivity in the synthesis of hydroxycinnamate saccharide esters. These compounds are interesting because of their amphiphilicity and antioxidative potential. Synthetic reactions using mono- or disaccharides as one of the substrates may moreover direct new routes for biomass upgrading in the biorefinery. The paper reviews the available data for enzymatic hydroxycinnamate saccharide ester synthesis in organic solvent systems as well as other enzymatic hydroxycinnamate acylations in ionic liquid systems. The choice of solvent system is highly decisive for enzyme stability, selectivity, and reaction yields in these synthesis reactions. To increase the understanding of the reaction environment and to facilitate solvent screening as a crucial part of the reaction design, the review explores the use of activity coefficient models for describing these systems and - more importantly - the use of group contribution model UNIFAC and quantum chemistry based COSMO-RS for thermodynamic predictions and preliminary solvent screening. Surfactant-free microemulsions of a hydrocarbon, a polar alcohol, and water are interesting solvent systems because they accommodate different substrate and product solubilities and maintain enzyme stability. Ionic liquids may provide advantages as solvents in terms of increased substrate and product solubility, higher reactivity and selectivity, as well as tunable physicochemical properties, but their design should be carefully considered in relation to enzyme stability. The treatise shows that thermodynamic modeling tools for solvent design provide a new toolbox to design enzyme-catalyzed synthetic reactions from biomass sources. Copyright © 2011 Elsevier B.V. All rights reserved.

Spiral computed tomography assessment of the efficacy of different rotary versus hand retreatment system.

PubMed

Mittal, Neelam; Jain, Jyoti

2014-01-01

The purpose of this study was to evaluate the efficacy of nickel-titanium rotary retreatment systems versus stainless steel hand retreatment system with or without solvent for gutta-percha removal during retreatment. Sixty extracted human mandibular molar teeth with single canal in a distal root was prepared with ProTaper rotary nickel-titanium files and obturated with gutta-percha and sealer. The teeth were randomly divided into six groups of 10 specimens in each groups. The volume of filling material before and after retreatment were evaluated in cm(3) using the computed tomography (CT) scanner proprietary software. Maximum amount of filling material removed during retreatment with ProTaper retreatment system with solvent and minimum with hand retreatment system with solvent. None of the technique was 100% effective in removing the filling materials, but the ProTaper retreatment system with solvent was better.

Molecular microenvironments: Solvent interactions with nucleic acid bases and ions

NASA Technical Reports Server (NTRS)

Macelroy, R. D.; Pohorille, A.

1986-01-01

The possibility of reconstructing plausible sequences of events in prebiotic molecular evolution is limited by the lack of fossil remains. However, with hindsight, one goal of molecular evolution was obvious: the development of molecular systems that became constituents of living systems. By understanding the interactions among molecules that are likely to have been present in the prebiotic environment, and that could have served as components in protobiotic molecular systems, plausible evolutionary sequences can be suggested. When stable aggregations of molecules form, a net decrease in free energy is observed in the system. Such changes occur when solvent molecules interact among themselves, as well as when they interact with organic species. A significant decrease in free energy, in systems of solvent and organic molecules, is due to entropy changes in the solvent. Entropy-driven interactioins played a major role in the organization of prebiotic systems, and understanding the energetics of them is essential to understanding molecular evolution.

HPLC-MS/MS analysis of anthocyanins in human plasma and urine using protein precipitation and dilute-and-shoot sample preparation methods, respectively.

PubMed

Liu, Junguo; Song, Jiuxue; Huang, Karen; Michel, Deborah; Fang, Jim

2018-05-01

A high-performance liquid chromatography tandem-mass spectrometry (HPLC-MS/MS) method has been developed to analyze anthocyanins in urine and plasma to further understand their absorption, distribution, metabolism and excretion. The method employed a Synergi RP-Max column (250 × 4.6 mm, 4 μm) and an API 4000 mass spectrometer. A gradient elution system consisted of mobile phase A (water-1% formic acid) and mobile phase B (acetonitrile) with a flow rate of 0.60 mL/min. The gradient was initiated at 5% B, increased to 21% B at 20 min, and then increased to 40% B at 35 min. The analysis of anthocyanins presents a challenge because of the poor stability of anthocyanins during sample preparation, especially during solvent evaporation. In this method, the degradation of anthocyanins was minimized using protein precipitation and dilute-and-shoot and sample preparation methods for plasma and urine, respectively. No interferences were observed from endogenous compounds. The method has been used to analyze anthocyanin concentrations in urine and plasma samples from volunteers administered saskatoon berries. Cyanidin-3-galactoside, cyanidin-3-glucoside, cyanidin-3-arabinoside, cyanidin-3-xyloside and quercetin-3-galactoside, the five major flavonoid components in saskatoon berries, were identified in plasma and urine samples. Copyright © 2017 John Wiley & Sons, Ltd.

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

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

Pierleoni, Davide; Minelli, Matteo; Doghieri, Ferruccio

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

Bench-Scale Silicone Process for Low-Cost CO{sub 2} Capture

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

Vipperla, Ravikumar; Yee, Michael; Steele, Ray

This report presents system and economic analysis for a carbon capture unit which uses an amino-silicone solvent for CO{sub 2} capture and sequestration (CCS) in a pulverized coal (PC) boiler. The amino-silicone solvent is based on GAP-1 with tri-ethylene glycol (TEG) as a co-solvent. For comparison purposes, the report also shows results for a CCS unit based on a conventional approach using mono-ethanol amine (MEA). At a steam temperature of 395 °C (743 °F), the CCS energy penalty for amino-silicone solvent is only 30.4% which compares to a 35.9% energy penalty for MEA. The increase in COE for the amino-siliconemore » solvent relative to the non-capture case is between 98% and 103% (depending on the solvent cost) which compares to an ~109% COE cost increase for MEA. In summary, the amino-silicone solvent has significant advantages over conventional systems using MEA.« less

INVESTIGATION OF A MIXTURE CONTAINING ALPRAZOLAM, CODEINE AND PARACETAMOL USING THIN-LAYER AND HIGH PERFORMANCE LIQUID CHROMATOGRAPHY METHODS.

PubMed

Ciegis, Paulius; Zevzikovas, Andrejus; Zevzikoviene, Augusta; Nenortiene, Palma; Kazlauskiene, Daiva

2016-01-01

The increasing drug consumption in Lithuania and all over the world makes us think about the negative consequences - the risk of toxicity. Fast and accurate identification of material that caused the poisoning reduces the probability in death cases and makes easier to determine the main cause of death. The results have shown that the most appropriate systems of solvents for qualitative analysis by TLC method of the mixture consisting of alprazolam, codeine and paracetanol are: system "D" (trichloromethane : acetone : conc. ammonia = 55 : 40 : 5 (v/v/v)) and system "F" (trichloromethane : diethyl ether: isobutanol : conc. ammonia = 50 : 30 : 15 : 5 (v/v/v/v)). For qualitative analysis of the mixture consisting of alprazolam, codeine and paracetamol by HPLC method the chromatographic column ACE C18 (25 cm x 4.6 mm x 5 µm), gradient elution mode (mixture of 3% acetic acid and methanol and the flow rate 1 mL/min have been used. The injection volume was 10 pL. Photodiode array detector (210 - 240 nm range) has been used. UV absorption spectra of materials measured using photodiode array detector have been identical to those presented in the scientific literature.

Organic solvents, electrolytes, and lithium ion cells with good low temperature performance

NASA Technical Reports Server (NTRS)

Huang, Chen-Kuo (Inventor); Smart, Marshall C. (Inventor); Surampudi, Subbarao (Inventor); Bugga, Ratnakumar V. (Inventor)

2002-01-01

Multi-component organic solvent systems, electrolytes and electrochemical cells characterized by good low temperature performance are provided. In one embodiment, an improved organic solvent system contains a ternary mixture of ethylene carbonate, dimethyl carbonate and diethyl carbonate. In other embodiments, quaternary systems include a fourth component, i.e, an aliphatic ester, an asymmetric alkyl carbonate or a compound of the formula LiOX, where X is R, COOR, or COR, where R is alkyl or fluoroalkyl. Electrolytes based on such organic solvent systems are also provided and contain therein a lithium salt of high ionic mobility, such as LiPF.sub.6. Reversible electrochemical cells, particularly lithium ion cells, are constructed with the improved electrolytes, and preferably include a carbonaceous anode, an insertion type cathode, and an electrolyte interspersed therebetween.

40 CFR 60.434 - Monitoring of operations and recordkeeping.

Code of Federal Regulations, 2011 CFR

2011-07-01

... recordkeeping. 60.434 Section 60.434 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR... affected facility using waterborne ink systems or solvent-borne ink systems with solvent recovery systems...) If affected facilities share the same raw ink storage/handling system with existing facilities...

40 CFR 60.434 - Monitoring of operations and recordkeeping.

Code of Federal Regulations, 2010 CFR

2010-07-01

... recordkeeping. 60.434 Section 60.434 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR... affected facility using waterborne ink systems or solvent-borne ink systems with solvent recovery systems...) If affected facilities share the same raw ink storage/handling system with existing facilities...

Solvent-Polarity-Induced Active Layer Morphology Control in Crystalline Diketopyrrolopyrrole-Based Low Band Gap Polymer Photovoltaics

NASA Astrophysics Data System (ADS)

Ferdous, Sunzida; Liu, Feng; Wang, Dong; Russell, Thomas

2014-03-01

The effects of various processing solvents on the morphology of diketopyrrolopyrrole (DPP)-based low band gap polymer (PDPPBT) and phenyl-C71-butyric acid methyl ester (PC71BM) blends are studied. The quality of the processing solvents was varied systematically using a mixture of a non-aromatic polar primary solvent with high boiling point secondary solvents of increasing polarities. An unfavorable solvent-PC71BM interaction affects the growth process of polymer crystallites inside the blend. When non-aromatic polar solvent was used, large PC71BM aggregates were formed that increase in size with the addition of non-polar secondary solvents. When polar solvents were instead used as the secondary solvents, the size scales of the aggregates decrease markedly, creating a percolated fibrillar network. Power conversion efficiencies of 0.03% to 5% are obtained, depending on the solvent system used.

Solvent Boundary Potentials for Hybrid QM/MM Computations Using Classical Drude Oscillators: A Fully Polarizable Model.

PubMed

Boulanger, Eliot; Thiel, Walter

2012-11-13

Accurate quantum mechanical/molecular mechanical (QM/MM) treatments should account for MM polarization and properly include long-range electrostatic interactions. We report on a development that covers both these aspects. Our approach combines the classical Drude oscillator (DO) model for the electronic polarizability of the MM atoms with the generalized solvent boundary Potential (GSBP) and the solvated macromolecule boundary potential (SMBP). These boundary potentials (BP) are designed to capture the long-range effects of the outer region of a large system on its interior. They employ a finite difference approximation to the Poisson-Boltzmann equation for computing electrostatic interactions and take into account outer-region bulk solvent through a polarizable dielectric continuum (PDC). This approach thus leads to fully polarizable three-layer QM/MM-DO/BP methods. As the mutual responses of each of the subsystems have to be taken into account, we propose efficient schemes to converge the polarization of each layer simultaneously. For molecular dynamics (MD) simulations using GSBP, this is achieved by considering the MM polarizable model as a dynamical degree of freedom, and hence contributions from the boundary potential can be evaluated for a frozen state of polarization at every time step. For geometry optimizations using SMBP, we propose a dual self-consistent field approach for relaxing the Drude oscillators to their ideal positions and converging the QM wave function with the proper boundary potential. The chosen coupling schemes are evaluated with a test system consisting of a glycine molecule in a water ball. Both boundary potentials are capable of properly reproducing the gradients at the inner-region atoms and the Drude oscillators. We show that the effect of the Drude oscillators must be included in all terms of the boundary potentials to obtain accurate results and that the use of a high dielectric constant for the PDC does not lead to a polarization catastrophe of the DO models. Optimum values for some key parameters are discussed. We also address the efficiency of these approaches compared to standard QM/MM-DO calculations without BP. In the SMBP case, computation times can be reduced by around 40% for each step of a geometry optimization, with some variation depending on the chosen QM method. In the GSBP case, the computational advantages of using the boundary potential increase with system size and with the number of MD steps.

Models for liquid-liquid partition in the system dimethyl sulfoxide-organic solvent and their use for estimating descriptors for organic compounds.

PubMed

Karunasekara, Thushara; Poole, Colin F

2011-07-15

Partition coefficients for varied compounds were determined for the organic solvent-dimethyl sulfoxide biphasic partition system where the organic solvent is n-heptane or isopentyl ether. These partition coefficient databases are analyzed using the solvation parameter model facilitating a quantitative comparison of the dimethyl sulfoxide-based partition systems with other totally organic partition systems. Dimethyl sulfoxide is a moderately cohesive solvent, reasonably dipolar/polarizable and strongly hydrogen-bond basic. Although generally considered to be non-hydrogen-bond acidic, analysis of the partition coefficient database strongly supports reclassification as a weak hydrogen-bond acid in agreement with recent literature. The system constants for the n-heptane-dimethyl sulfoxide biphasic system provide an explanation of the mechanism for the selective isolation of polycyclic aromatic compounds from mixtures containing low-polarity hydrocarbons based on the capability of the polar interactions (dipolarity/polarizability and hydrogen-bonding) to overcome the opposing cohesive forces in dimethyl sulfoxide that are absent for the interactions with hydrocarbons of low polarity. In addition, dimethyl sulfoxide-organic solvent systems afford a complementary approach to other totally organic biphasic partition systems for descriptor measurements of compounds virtually insoluble in water. Copyright © 2011 Elsevier B.V. All rights reserved.

Computational screening of biomolecular adsorption and self-assembly on nanoscale surfaces.

PubMed

Heinz, Hendrik

2010-05-01

The quantification of binding properties of ions, surfactants, biopolymers, and other macromolecules to nanometer-scale surfaces is often difficult experimentally and a recurring challenge in molecular simulation. A simple and computationally efficient method is introduced to compute quantitatively the energy of adsorption of solute molecules on a given surface. Highly accurate summation of Coulomb energies as well as precise control of temperature and pressure is required to extract the small energy differences in complex environments characterized by a large total energy. The method involves the simulation of four systems, the surface-solute-solvent system, the solute-solvent system, the solvent system, and the surface-solvent system under consideration of equal molecular volumes of each component under NVT conditions using standard molecular dynamics or Monte Carlo algorithms. Particularly in chemically detailed systems including thousands of explicit solvent molecules and specific concentrations of ions and organic solutes, the method takes into account the effect of complex nonbond interactions and rotational isomeric states on the adsorption behavior on surfaces. As a numerical example, the adsorption of a dodecapeptide on the Au {111} and mica {001} surfaces is described in aqueous solution. Copyright 2009 Wiley Periodicals, Inc.

Zero-Valent Metallic Treatment System and Its Application for Removal and Remediation of Polychlorinated Biphenyls (Pcbs)

NASA Technical Reports Server (NTRS)

Clausen, Christian A. (Inventor); Geiger, Cherie L. (Inventor); Quinn, Jacqueline W. (Inventor); Brooks, Kathleen B. (Inventor)

2012-01-01

PCBs are removed from contaminated media using a treatment system including zero-valent metal particles and an organic hydrogen donating solvent. The treatment system may include a weak acid in order to eliminate the need for a coating of catalytic noble metal on the zero-valent metal particles. If catalyzed zero-valent metal particles are used, the treatment system may include an organic hydrogen donating solvent that is a non-water solvent. The treatment system may be provided as a "paste-like" system that is preferably applied to natural media and ex-situ structures to eliminate PCBs.

Ozonation of Canadian Athabasca asphaltene

NASA Astrophysics Data System (ADS)

Cha, Zhixiong

Application of ozonation in the petrochemical industry for heavy hydrocarbon upgrading has not been sufficiently explored. Among heavy hydrocarbons, asphaltenes are the heaviest and the most difficult fractions for analysis and treatment. Therefore, ozonation of asphaltenes presents an interesting application in the petrochemical industry. Commercial application of ozonation in the petrochemical industry has three obstacles: availability of an ozone-resistant and environmentally friendly solvent, the precipitation of ozonation intermediates during reaction, and recovery of the solvent and separation of the ozonation products. Preliminary ozonation of Athabasca oil sands asphaltene in nonparticipating solvents encountered serious precipitation of the ozonation intermediates. The precipitated intermediates could be polymeric ozonides and intermolecular ozonides or polymeric peroxides. Because the inhomogeneous reaction medium caused low ozone efficiency, various participating solvents such as methanol and acetic acid were added to form more soluble hydroperoxides. The mass balance results showed that on average, one asphaltene molecule reacted with 12 ozone molecules through the electrophilic reaction and the subsequent decomposition of ozonation intermediates generated acetone extractable products. GC/MS analysis of these compounds indicated that the free radical reactions could be important for generation of volatile products. The extensively ozonated asphaltene in the presence of participating solvents were refluxed with methanol to generate more volatile products. GC/MS analysis of the methanol-esterified ozonation products indicated that most volatile products were aliphatic carboxylic acid esters generated through cleavage of substituents. Reaction kinetics study showed that asphaltene ozonation was initially a diffusion rate-controlled reaction and later developed to a chemical reaction rate-controlled reaction after depletion of the reactive aromatic sites. Two new solvent systems, a self-sustaining ozonation system and a cyclohexane/acetone/water or a cyclohexane/acetone/methanol system, were studied to overcome the drawback of using halogenated solvents. The self-sustaining ozonation process employed the final ozonation products as the reaction solvent. Compared to the self-sustaining ozonation, the cyclohexane solvent system showed higher ozone efficiency; however, it required dynamic adjustment of the solvent system during ozonation. An extensively ozonated asphaltene's weight would be doubled. Distillation of the products separated about 45% volatile products having biodiesel-style chemical structures. Compared to distillation, more than 90% of the ozonation products were extractable by acetone. The remaining acetone-insoluble part was further classified by dichloromethane and other solvents of different polarities. The separated ozonation products were good fuel additives or materials for other products.

Pilot-Scale Silicone Process for Low-Cost Carbon Dioxide Capture Preliminary Techno-Economic Analysis

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

Singh, Surinder; Spiry, Irina; Wood, Benjamin

This report presents system and economic analysis for a carbon-capture unit which uses an aminosilicone-based solvent for CO{sub 2} capture in a pulverized coal (PC) boiler. The aminosilicone solvent is a 60/40 wt/wt mixture of 3-aminopropyl end-capped polydimethylsiloxane (GAP-1m) with tri-ethylene glycol (TEG) as a co-solvent. For comparison purposes, the report also shows results for a carbon-capture unit based on a conventional approach using mono-ethanol amine (MEA). The first year removal cost of CO{sub 2} for the aminosilicone-based carbon-capture process ismore » $46.04/ton of CO2 as compared to $$60.25/ton of CO{sub 2} when MEA is used. The aminosilicone-based process has <77% of the CAPEX of a system using MEA solvent. The lower CAPEX is due to several factors, including the higher working capacity of the aminosilicone solvent compared the MEA, which reduces the solvent flow rate required, reducing equipment sizes. If it is determined that carbon steel can be used in the rich-lean heat exchanger in the carbon capture unit, the first year removal cost of CO{sub 2} decreases to $$44.12/ton. The aminosilicone-based solvent has a higher thermal stability than MEA, allowing desorption to be conducted at higher temperatures and pressures, decreasing the number of compressor stages needed. The aminosilicone-based solvent also has a lower vapor pressure, allowing the desorption to be conducted in a continuous-stirred tank reactor versus a more expensive packed column. The aminosilicone-based solvent has a lower heat capacity, which decreases the heat load on the desorber. In summary, the amino-silicone solvent has significant advantages over conventional systems using MEA.« less

Pilot-Scale Silicone Process for Low-Cost Carbon Dioxide Capture

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

Singh, Surinder; Spiry, Irina; Wood, Benjamin

This report presents system and economicanalysis for a carbon-capture unit which uses an aminosilicone-based solvent for CO₂ capture in a pulverized coal (PC) boiler. The aminosilicone solvent is a 60/40 wt/wt mixture of 3-aminopropyl end-capped polydimethylsiloxane (GAP-1m) with tri-ethylene glycol (TEG) as a co-solvent. Forcomparison purposes, the report also shows results for a carbon-capture unit based on a conventional approach using mono-ethanol amine (MEA). The first year removal cost of CO₂ for the aminosilicone-based carbon-capture process is $46.04/ton of CO₂ as compared to $60.25/ton of CO₂ when MEA is used. The aminosilicone- based process has <77% of the CAPEX ofmore » a system using MEA solvent. The lower CAPEX is due to several factors, including the higher working capacity of the aminosilicone solvent compared the MEA, which reduces the solvent flow rate required, reducing equipment sizes. If it is determined that carbon steel can be used in the rich-lean heat exchanger in the carbon capture unit, the first year removal cost of CO₂ decreases to $44.12/ton. The aminosilicone-based solvent has a higherthermal stability than MEA, allowing desorption to be conducted at higher temperatures and pressures, decreasing the number of compressor stages needed. The aminosilicone-based solvent also has a lowervapor pressure, allowing the desorption to be conducted in a continuous-stirred tank reactor versus a more expensive packed column. The aminosilicone-based solvent has a lowerheat capacity, which decreases the heat load on the desorber. In summary, the amino-silicone solvent has significant advantages overconventional systems using MEA.« less

Liquid filament instability due to stretch-induced phase separation in polymer solutions

NASA Astrophysics Data System (ADS)

Arinstein, Arkadii; Kulichikhin, Valery; Malkin, Alexander; Technion-Israel Institute of Technology Collaboration; Institute of Petrochemical Synthesis, Russian Academy of Sciences Team

2015-03-01

The instability in a jet of a viscoelastic semi-dilute entangled polymer solution under high stretching is discussed. Initially, the variation in osmotic pressure can compensate for decrease in the capillary force, and the jet is stable. The further evolution of the polymer solution along the jet results in formation of a filament in the jet center and of a near-surface solvent layer. Such a redistribution of polymer seems like a ``phase separation'', but it is related to stretching of the jet. The viscous liquid shell demonstrates Raleigh-type instability resulting in the formation of individual droplets on the oriented filament. Experimental observations showed that this separation is starting during few first seconds, and continues of about 10 -15 seconds. The modeling shows that a jet stretching results in a radial gradient in the polymer distribution: the polymer is concentrated in the jet center, whereas the solvent is remaining near the surface. The key point of this model is that a large longitudinal stretching of a polymer network results in its lateral contraction, so a solvent is pressed out of this polymer network because of the decrease in its volume. V.K. and A.M. acknowledge the financial support of the Russian Scientific Foundation (Grant 4-23-00003).

Isolation and identification of fatty acid amides from Shengli coal

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

Ming-Jie Ding; Zhi-Min Zong; Ying Zong

Shengli coal, a Chinese brown coal, was extracted with carbon disulfide and the extract was gradiently eluted with n-hexane and ethyl acetate (EA)/n-hexane mixed solvents with different concentrations of EA in a silica gel-filled column. A series of fatty acid amides, including fourteen alkanamides (C{sub 15}-C{sub 28}) and three alkenamides (C{sub 18} and C{sub 22}), were isolated from the coal by this method and analyzed with a gas chromatography/mass spectrometry. 26 refs., 2 figs., 2 tabs.

Separation of aromatic carboxylic acids using quaternary ammonium salts on reversed-phase HPLC. 2. Application for the analysis of Loy Yang coal oxidation products

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

Kawamura, K.; Okuwaki, A.; Verheyen, T.V.

In order to develop separation processes and analytical methods for aromatic carboxylic acids for the coal oxidation products, the separation behavior of aromatic carboxylic acids on a reversed-phase HPLC using eluent containing quaternary ammonium salt was optimized using the solvent gradient method. This method was applied for the analysis of Loy Yang coal oxidation products. It was confirmed that the analytical data using this method were consistent with those determined using gas chromatography.

Organic fluid permeation through fluoropolymer membranes

DOEpatents

Nemser, Stuart M.; Kosaraju, Praveen; Bowser, John

2015-07-14

Separation of the components of liquid mixtures is achieved by contacting a liquid mixture with a nonporous membrane having a fluoropolymer selectively permeable layer and imposing a pressure gradient across the membrane from feed side to permeate side. Unusually high transmembrane flux is obtained when the membrane is subjected to one or more process conditions prior to separation. These include (a) leaving some residual amount of membrane casting solvent in the membrane, and (b) contacting the membrane with a component of the mixture to be separated for a duration effective to saturate the membrane with the component.

Single column comprehensive analysis of pharmaceutical preparations using dual-injection mixed-mode (ion-exchange and reversed-phase) and hydrophilic interaction liquid chromatography.

PubMed

Kazarian, Artaches A; Taylor, Mark R; Haddad, Paul R; Nesterenko, Pavel N; Paull, Brett

2013-12-01

The comprehensive separation and detection of hydrophobic and hydrophilic active pharmaceutical ingredients (APIs), their counter-ions (organic, inorganic) and excipients, using a single mixed-mode chromatographic column, and a dual injection approach is presented. Using a mixed-mode Thermo Fisher Acclaim Trinity P1 column, APIs, their counter-ions and possible degradants were first separated using a combination of anion-exchange, cation-exchange and hydrophobic interactions, using a mobile phase consisting of a dual organic modifier/salt concentration gradient. A complementary method was also developed using the same column for the separation of hydrophilic bulk excipients, using hydrophilic interaction liquid chromatography (HILIC) under high organic solvent mobile phase conditions. These two methods were then combined within a single gradient run using dual sample injection, with the first injection at the start of the applied gradient (mixed-mode retention of solutes), followed by a second sample injection at the end of the gradient (HILIC retention of solutes). Detection using both ultraviolet absorbance and refractive index enabled the sensitive detection of APIs and UV-absorbing counter-ions, together with quantitative determination of bulk excipients. The developed approach was applied successfully to the analysis of a dry powder inhalers (Flixotide(®), Spiriva(®)), enabling comprehensive quantification of all APIs and excipients in the sample. Copyright © 2013 Elsevier B.V. All rights reserved.

The Ideal Solvent for Paper Chromatography of Food Dyes.

ERIC Educational Resources Information Center

Markow, Peter G.

1988-01-01

Uses paper chromatography with food dyes to provide a simple and inexpensive basis for teaching chromatography. Provides experimental methodology and tabled results. Includes a solvent system comparison (Rf) for seven dyes and twenty-two solvents. (MVL)

Opportunities for Bio-Based Solvents Created as Petrochemical and Fuel Products Transition towards Renewable Resources

PubMed Central

Clark, James H.; Farmer, Thomas J.; Hunt, Andrew J.; Sherwood, James

2015-01-01

The global bio-based chemical market is growing in size and importance. Bio-based solvents such as glycerol and 2-methyltetrahydrofuran are often discussed as important introductions to the conventional repertoire of solvents. However adoption of new innovations by industry is typically slow. Therefore it might be anticipated that neoteric solvent systems (e.g., ionic liquids) will remain niche, while renewable routes to historically established solvents will continue to grow in importance. This review discusses bio-based solvents from the perspective of their production, identifying suitable feedstocks, platform molecules, and relevant product streams for the sustainable manufacturing of conventional solvents. PMID:26225963

Opportunities for Bio-Based Solvents Created as Petrochemical and Fuel Products Transition towards Renewable Resources.

PubMed

Clark, James H; Farmer, Thomas J; Hunt, Andrew J; Sherwood, James

2015-07-28

The global bio-based chemical market is growing in size and importance. Bio-based solvents such as glycerol and 2-methyltetrahydrofuran are often discussed as important introductions to the conventional repertoire of solvents. However adoption of new innovations by industry is typically slow. Therefore it might be anticipated that neoteric solvent systems (e.g., ionic liquids) will remain niche, while renewable routes to historically established solvents will continue to grow in importance. This review discusses bio-based solvents from the perspective of their production, identifying suitable feedstocks, platform molecules, and relevant product streams for the sustainable manufacturing of conventional solvents.

Magnetic nanoparticles and high-speed countercurrent chromatography coupled in-line and using the same solvent system for separation of quercetin-3-O-rutinoside, luteoloside and astragalin from a Mikania micrantha extract.

PubMed

Wang, Juanqiang; Geng, Shan; Wang, Binghai; Shao, Qian; Fang, Yingtong; Wei, Yun

2017-07-28

A new in-line method of magnetic nanoparticles (MNPs) coupled with high-speed countercurrent chromatography (HSCCC) using a same solvent system during the whole separation process was established to achieve the rapid separation of flavonoids from Mikania micrantha. The adsorption and desorption capacities of five different MNPs for flavonoid standards and Mikania micrantha crude extract were compared and the most suitable magnetic nanoparticle Fe 3 O 4 @SiO 2 @DIH@EMIMLpro was selected as the in-line MNP column. An in-line separation system was established by combining this MNP column with HSCCC through a six-way valve. The comparison between two solvent systems n-hexane-ethyl acetate-methanol-water (3:5:3:5, v/v) and ethyl acetate-methanol-water (25:1:25, v/v) showed that the latter solvent system was more suitable for simultaneously in-line separating three flavonoids quercetin-3-O-rutinoside, luteoloside and astragalin from Mikania micrantha. The purities of these three compounds with the ethyl acetate-methanol-water solvent system were 95.13%, 98.54% and 98.19% respectively. Results showed the established in-line separation system of MNP-HSCCC was efficient, recyclable and served to isolate potential flavonoids with similar polarities from natural complex mixtures. The in-line combination of magnetic nanoparticles with high-speed countercurrent chromatography eluting with the same solvent system during the whole separation process was established for the first time. Copyright © 2017 Elsevier B.V. All rights reserved.

The salinity gradient power generating system integrated into the seawater desalination system

NASA Astrophysics Data System (ADS)

Zhu, Yongqiang; Wang, Wanjun; Cai, Bingqian; Hao, Jiacheng; Xia, Ruihua

2017-01-01

Seawater desalination is an important way to solve the problem of fresh water shortage. Low energy efficiency and high cost are disadvantages existing in seawater desalination. With huge reserve and the highest energy density among different types of marine energy, salinity gradient energy has a bright application prospect. The promotion of traditional salinity gradient power generating systems is hindered by its low efficiency and specific requirements on site selection. This paper proposes a salinity gradient power generating system integrated into the seawater desalination system which combines the salinity gradient power generating system and the seawater desalination system aiming to remedy the aforementioned deficiency and could serve as references for future seawater desalination and salinity gradient energy exploitation. The paper elaborates on the operating principles of the system, analyzes the detailed working process, and estimates the energy output and consumption of the system. It is proved that with appropriate design, the energy output of the salinity gradient power generating system can satisfy the demand of the seawater desalination system.

Diffusion of Small Solute Particles in Viscous Liquids: Cage Diffusion, a Result of Decoupling of Solute-Solvent Dynamics, Leads to Amplification of Solute Diffusion.

PubMed

Acharya, Sayantan; Nandi, Manoj K; Mandal, Arkajit; Sarkar, Sucharita; Bhattacharyya, Sarika Maitra

2015-08-27

We study the diffusion of small solute particles through solvent by keeping the solute-solvent interaction repulsive and varying the solvent properties. The study involves computer simulations, development of a new model to describe diffusion of small solutes in a solvent, and also mode coupling theory (MCT) calculations. In a viscous solvent, a small solute diffuses via coupling to the solvent hydrodynamic modes and also through the transient cages formed by the solvent. The model developed can estimate the independent contributions from these two different channels of diffusion. Although the solute diffusion in all the systems shows an amplification, the degree of it increases with solvent viscosity. The model correctly predicts that when the solvent viscosity is high, the solute primarily diffuses by exploiting the solvent cages. In such a scenario the MCT diffusion performed for a static solvent provides a correct estimation of the cage diffusion.

Coal liquefaction in an inorganic-organic medium. [DOE patent application

DOEpatents

Vermeulen, T.; Grens, E.A. II; Holten, R.R.

Improved process for liquefaction of coal by contacting pulverized coal in an inorganic-organic medium solvent system containing a ZnCl/sub 2/ catalyst, a polar solvent with the structure RX where X is one of the elements O, N, S, or P, and R is hydrogen or a lower hydrocarbon radical; the solvent system can contain a hydrogen donor solvent (and must when RX is water) which is immiscible in the ZnCl/sub 2/ and is a hydroaromatic hydrocarbon selected from tetralin, dihydrophenanthrene, dihydroanthracene or a hydrogenated coal derived hydroaromatic hydrocarbon distillate fraction.

High performance liquid chromatography hyphenated to inductively coupled plasma mass spectrometry for V and Ni quantification as tetrapyrroles

NASA Astrophysics Data System (ADS)

Duyck, Christiane Béatrice; Saint'Pierre, Tatiana Dillenburg; Miekeley, Norbert; da Fonseca, Teresa Cristina Oliveira; Szatmari, Peter

2011-05-01

A method was developed for the determination of V and Ni as tetrapyrroles by High Performance Liquid Chromatography hyphenated to Inductively Coupled Plasma Mass Spectrometry (HPLC-ICP-MS) using reversed phase and elution gradient. Chlorinated solvents and tetrahydrofuran were investigated as regard to separation time and ICP-MS detection efficiencies. The final elution gradient program started from pure methanol to a mixture of 20:80 (v/v) chloroform:methanol. External quantification of V and Ni with inorganic standards by flow injection ICP-MS, used online with HPLC, resulted in 95% of recoveries. The Limits of Detection for V during methanol elution and for Ni during the 20% chloroform gradient elution were evaluated by their minimum detectable concentrations, which were, respectively, 5 μg L - 1 and 8 μg L - 1 . The methodology was applied to polar and resin fractions separated from a Brazilian crude oil and a sediment extract from an oil-polluted area in the Guanabara Bay, Rio de Janeiro, Brazil. Vanadium as tetrapyrroles represented the totality of V content in the polar fraction, whereas Ni was in different polar forms in the resin and sediment extract.

Joint density-functional theory for energetics and spectroscopy in complex aqueous and nonaqueous solvents

NASA Astrophysics Data System (ADS)

Gunceler, Deniz

Solvents are of great importance in many technological applications, but are difficult to study using standard, off-the-shelf ab initio electronic structure methods. This is because a single configuration of molecular positions in the solvent (a "snapshot" of the fluid) is not necessarily representative of the thermodynamic average. To obtain any thermodynamic averages (e.g. free energies), the phase space of the solvent must be sampled, typically using molecular dynamics. This greatly increases the computational cost involved in studying solvated systems. Joint density-functional theory has made its mark by being a computationally efficient yet rigorous theory by which to study solvation. It replaces the need for thermodynamic sampling with an effective continuum description of the solvent environment that is in-principle exact, computationally efficient and intuitive (easier to interpret). It has been very successful in aqueous systems, with potential applications in (among others) energy materials discovery, catalysis and surface science. In this dissertation, we develop accurate and fast joint density functional theories for complex, non-aqueous solvent enviroments, including organic solvents and room temperature ionic liquids, as well as new methods for calculating electron excitation spectra in such systems. These theories are then applied to a range of physical problems, from dendrite formation in lithium-metal batteries to the optical spectra of solvated ions.

Development of Simulation Methods in the Gibbs Ensemble to Predict Polymer-Solvent Phase Equilibria

NASA Astrophysics Data System (ADS)

Gartner, Thomas; Epps, Thomas; Jayaraman, Arthi

Solvent vapor annealing (SVA) of polymer thin films is a promising method for post-deposition polymer film morphology control. The large number of important parameters relevant to SVA (polymer, solvent, and substrate chemistries, incoming film condition, annealing and solvent evaporation conditions) makes systematic experimental study of SVA a time-consuming endeavor, motivating the application of simulation and theory to the SVA system to provide both mechanistic insight and scans of this wide parameter space. However, to rigorously treat the phase equilibrium between polymer film and solvent vapor while still probing the dynamics of SVA, new simulation methods must be developed. In this presentation, we compare two methods to study polymer-solvent phase equilibrium-Gibbs Ensemble Molecular Dynamics (GEMD) and Hybrid Monte Carlo/Molecular Dynamics (Hybrid MC/MD). Liquid-vapor equilibrium results are presented for the Lennard Jones fluid and for coarse-grained polymer-solvent systems relevant to SVA. We found that the Hybrid MC/MD method is more stable and consistent than GEMD, but GEMD has significant advantages in computational efficiency. We propose that Hybrid MC/MD simulations be used for unfamiliar systems in certain choice conditions, followed by much faster GEMD simulations to map out the remainder of the phase window.

Combining the ensemble and Franck-Condon approaches for calculating spectral shapes of molecules in solution

NASA Astrophysics Data System (ADS)

Zuehlsdorff, T. J.; Isborn, C. M.

2018-01-01

The correct treatment of vibronic effects is vital for the modeling of absorption spectra of many solvated dyes. Vibronic spectra for small dyes in solution can be easily computed within the Franck-Condon approximation using an implicit solvent model. However, implicit solvent models neglect specific solute-solvent interactions on the electronic excited state. On the other hand, a straightforward way to account for solute-solvent interactions and temperature-dependent broadening is by computing vertical excitation energies obtained from an ensemble of solute-solvent conformations. Ensemble approaches usually do not account for vibronic transitions and thus often produce spectral shapes in poor agreement with experiment. We address these shortcomings by combining zero-temperature vibronic fine structure with vertical excitations computed for a room-temperature ensemble of solute-solvent configurations. In this combined approach, all temperature-dependent broadening is treated classically through the sampling of configurations and quantum mechanical vibronic contributions are included as a zero-temperature correction to each vertical transition. In our calculation of the vertical excitations, significant regions of the solvent environment are treated fully quantum mechanically to account for solute-solvent polarization and charge-transfer. For the Franck-Condon calculations, a small amount of frozen explicit solvent is considered in order to capture solvent effects on the vibronic shape function. We test the proposed method by comparing calculated and experimental absorption spectra of Nile red and the green fluorescent protein chromophore in polar and non-polar solvents. For systems with strong solute-solvent interactions, the combined approach yields significant improvements over the ensemble approach. For systems with weak to moderate solute-solvent interactions, both the high-energy vibronic tail and the width of the spectra are in excellent agreement with experiments.

Solvent effects of a dimethyldicyanoquinonediimine buffer layer as N-type material on the performance of organic photovoltaic cells.

PubMed

Yang, Eui Yeol; Oh, Se Young

2014-08-01

In the present work, we have fabricated organic photovoltaic cells consisting of ITO/PEDOT:PSS/P3HT:PCBM/DMDCNQI/Al using a dip-coating method with various solvent systems. We have investigated solvent effects (such as solubility, viscosity and vapor pressure) in deposition of a thin DMDCNQI buffer layer on the performance of organic photovoltaic cells. The solvent system which had low viscosity and good solubility properties, made a dense and uniform DMDCNQI ultra thin film, resulting in a high performance device. In particular, a prepared organic photovoltaic cell was fabricated using a cosolvent system (methanol:methylenechloride = 3:1) and showed a maximum power conversion efficiency of 4.53%.

Bench-Scale Silicone Process for Low-Cost CO{sub 2} Capture

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

Vipperla, Ravikumar; Yee, Michael; Steele, Ray

This report presents system and economic analysis for a carbon capture unit which uses an amino-silicone solvent for CO{sub 2} capture and sequestration (CCS) in a pulverized coal (PC) boiler. The amino-silicone solvent is based on GAP-1 with Tri-Ethylene Glycol (TEG) as a co-solvent. The report also shows results for a CCS unit based on a conventional approach using mono-ethanol amine (MEA). Models were developed for both processes and used to calculate mass and energy balances. Capital costs and energy penalty were calculated for both systems, as well as the increase in cost of electricity. The amino-silicone solvent based systemmore » demonstrates significant advantages compared to the MEA system.« less

Development and validation of a liquid chromatographic method for the simultaneous determination of aniracetam and its related substances in the bulk drug and a tablet formulation.

PubMed

Papandreou, Georgios; Zorpas, Kostas; Archontaki, Helen

2011-11-01

Simultaneous determination of aniracetam and its related impurities (2-pyrrolidinone, p-anisic acid, 4-p-anisamidobutyric acid and (p-anisoyl)-4-methyl-2-pyrrolidinone) was accomplished in the bulk drug and in a tablet formulation using a high performance liquid chromatographic method with UV detection. Separation was achieved on a Hypersil BDS-CN column (150 mm × 4.0 mm, 5 μm) using a gradient elution program with solvent A composed of phosphate buffer (pH 4.0; 0.010 M) and solvent B of acetonitrile-phosphate buffer (pH 4.0; 0.010 M) (90:10, v/v). The flow rate of the mobile phase was 1.0 mL min(-1) and the total elution time, including the column re-equilibration, was approximately 20 min. The UV detection wavelength was varied appropriately among 210, 250 and 280 nm. Injection volume was 20 μL and experiments were conducted at ambient temperature. The developed method was validated in terms of system suitability, selectivity, linearity, range, precision, accuracy, limits of detection and quantification for the impurities, short term and long term stability of the analytes in the prepared solutions and robustness, following the ICH guidelines. Therefore, the proposed method was suitable for the simultaneous determination of aniracetam and its studied related impurities. Copyright © 2011 Elsevier B.V. All rights reserved.

Simultaneous quantitation of 14 active components in Yinchenhao decoction by using ultra high performance liquid chromatography with diode array detection: Method development and ingredient analysis of different commonly prepared samples.

PubMed

Yi, YaXiong; Zhang, Yong; Ding, Yue; Lu, Lu; Zhang, Tong; Zhao, Yuan; Xu, XiaoJun; Zhang, YuXin

2016-11-01

We developed a novel quantitative analysis method based on ultra high performance liquid chromatography coupled with diode array detection for the simultaneous determination of the 14 main active components in Yinchenhao decoction. All components were separated on an Agilent SB-C18 column by using a gradient solvent system of acetonitrile/0.1% phosphoric acid solution at a flow rate of 0.4 mL/min for 35 min. Subsequently, linearity, precision, repeatability, and accuracy tests were implemented to validate the method. Furthermore, the method has been applied for compositional difference analysis of 14 components in eight normal-extraction Yinchenhao decoction samples, accompanied by hierarchical clustering analysis and similarity analysis. The result that all samples were divided into three groups based on different contents of components demonstrated that extraction methods of decocting, refluxing, ultrasonication and extraction solvents of water or ethanol affected component differentiation, and should be related to its clinical applications. The results also indicated that the sample prepared by patients in the family by using water extraction employing a casserole was almost same to that prepared using a stainless-steel kettle, which is mostly used in pharmaceutical factories. This research would help patients to select the best and most convenient method for preparing Yinchenhao decoction. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Determination of 2,4-Dichlorophenoxyacetic acid (2,4-D) in rat serum for pharmacokinetic studies with a simple HPLC method

PubMed Central

Chen, Xiao; Wan, Yanjian; Chen, Xi; Li, Yuanyuan

2018-01-01

2,4-Dichlorophenoxyacetic acid (2,4-D) is a chlorophenoxy herbicide used worldwide. We describe a high-performance liquid chromatography (HPLC) method with UV detection for the determination of 2,4-D in female and male rat serum. This allows to observe the change of serum 2,4-D concentration in rats with time and its pharmacokinetics characteristics with a simple, rapid, optimized and validated method. The serum samples are pretreated and introduced into the HPLC system. The analytes are separated in a XDB-C18 column with a mobile phase of acetonitrile (solvent A) and 0.02 M ammonium acetate (containing 0.1% formic acid) (solvent B) using a gradient elution at a flow rate of 1.0 mL/min. The wavelength for UV detection was set at 230 nm. Calibration curve for 2,4-D was constructed over a range of 0.1–400 mg/L. The method was successfully applied to study the pharmacokinetics of 2,4-D in rats in this study. After oral administration of 300 mg/kg and 60 mg/kg 2,4-D, the mean Cmax values were 601.9 and 218.4 mg/L, the AUC0→∞ values were 23,722 and 4,127 mg×h/L and the clearance (Cl) were 1.10 and 0.02 L/(h×kg), respectively. The developed method was found to be specific, precise, reproducible and rapid. PMID:29342170

Determination of 2,4-Dichlorophenoxyacetic acid (2,4-D) in rat serum for pharmacokinetic studies with a simple HPLC method.

PubMed

Chen, Xiao; Zhang, Hongling; Wan, Yanjian; Chen, Xi; Li, Yuanyuan

2018-01-01

2,4-Dichlorophenoxyacetic acid (2,4-D) is a chlorophenoxy herbicide used worldwide. We describe a high-performance liquid chromatography (HPLC) method with UV detection for the determination of 2,4-D in female and male rat serum. This allows to observe the change of serum 2,4-D concentration in rats with time and its pharmacokinetics characteristics with a simple, rapid, optimized and validated method. The serum samples are pretreated and introduced into the HPLC system. The analytes are separated in a XDB-C18 column with a mobile phase of acetonitrile (solvent A) and 0.02 M ammonium acetate (containing 0.1% formic acid) (solvent B) using a gradient elution at a flow rate of 1.0 mL/min. The wavelength for UV detection was set at 230 nm. Calibration curve for 2,4-D was constructed over a range of 0.1-400 mg/L. The method was successfully applied to study the pharmacokinetics of 2,4-D in rats in this study. After oral administration of 300 mg/kg and 60 mg/kg 2,4-D, the mean Cmax values were 601.9 and 218.4 mg/L, the AUC0→∞ values were 23,722 and 4,127 mg×h/L and the clearance (Cl) were 1.10 and 0.02 L/(h×kg), respectively. The developed method was found to be specific, precise, reproducible and rapid.

SOLVENT EXTRACTION PROCESSES: A SURVEY OF SYSTEMS IN THE SITE PROGRAM

EPA Science Inventory

Solvent extraction of contaminated soils, sludges and sediments has been successfully completed at a number ofSuperfund sites. Each commercialized process uses a unique operating system to extract organic contaminants from solids. These operating systems may be classified by the ...

Performance of some DFT functionals with dispersion on modeling of the translational isomers of a solvent-switchable [2]rotaxane

NASA Astrophysics Data System (ADS)

Ivanov, Petko

2016-03-01

The balances of interactions were studied by computational methods in the translational isomers of a solvent switchable fullerene-stoppered [2]rotaxane (1) manifesting unexpected behavior, namely that due to favorable dispersion interactions the fullerene stopper becomes the second station upon change of the solvent. For comparison, another system, a pH switchable molecular shuttle (2), was also examined as an example of prevailing electrostatic interactions. Tested for 1 were five global hybrid Generalized Gradient Approximation functionals (B3LYP, B3LYP-D3, B3LYP-D3BJ, PBEh1PBE and APFD), one long-range corrected, range-separated functional with D2 empirical dispersion correction, ωB97XD, the Zhao-Truhlar's hybrid meta-GGA functional M06 with double the amount of nonlocal exchange (2X), and a pure functional, B97, with the Grimme's D3BJ dispersion (B97D3). The molecular mechanics method qualitatively correctly reproduced the behavior of the [2]rotaxanes, whereas the DFT models, except for M06-2X to some extent, failed in the case of significant dispersion interactions with participation of the fulleropyrrolidine stopper (rotaxane 1). Unexpectedly, the benzylic amide macrocycle tends to adopt preferentially 'boat'-like conformation in most of the cases. Four hydrogen bonds interconnect the axle with the wheel for the translational isomer with the macroring at the succinamide station (station II), whereas the number of hydrogen bonds vary for the isomer with the macroring at the fulleropyrrolidine stopper (station I) depending of the computational model used. The B3LYP and the PBEh1PBE results show strong preference of station II in the gas phase and in the model solvent DMSO. After including empirical dispersion correction, the translational isomer with the macroring at station I has the lower energy with B3LYP, both in the gas phase and in DMSO. The same result, but with higher preference of station I, was estimated with APFD, ωB97XD and B97D3. Only M06-2X presented qualitatively correct behavior for the relative stability of the two translational isomers, namely, slight preference of station II for the isolated molecule and higher relative energy of the same isomer with the model solvent DMSO. The electrostatic interactions in 2 have the decisive contribution both when the macroring is positioned at the dipeptide residue for the neutral form, and at the N-benzylalanine fragment after protonation, and the observed behavior of the [2]rotaxane is correctly reproduced by the methods used.

Femtosecond dynamics in hydrogen-bonded solvents

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

Castner, E.W. Jr.; Chang, Y.J.

1993-09-01

We present results on the ultrafast dynamics of pure hydrogen-bonding solvents, obtained using femtosecond Fourier-transform optical-heterodyne-detected, Raman-induced Kerr effect spectroscopy. Solvent systems we have studied include the formamides, water, ethylene glycol, and acetic acid. Inertial and diffusive motions are clearly resolved. We comment on the effect that such ultrafast solvent motions have on chemical reactions in solution.

Identification and quantification of 11-nor-Δ9-tetrahydrocannabinol-9-carboxylic acid glucuronide (THC-COOH-glu) in hair by ultra-performance liquid chromatography tandem mass spectrometry as a potential hair biomarker of cannabis use.

PubMed

Pichini, Simona; Marchei, Emilia; Martello, Simona; Gottardi, Massimo; Pellegrini, Manuela; Svaizer, Fiorenza; Lotti, Andrea; Chiarotti, Marcello; Pacifici, Roberta

2015-04-01

We developed and validated an ultra-high-pressure liquid chromatography-tandem mass spectrometry method to identify and quantify 11-nor-Δ9-tetrahydrocannabinol-9-carboxylic acid glucuronide in hair of cannabis consumers. After hair washing with methyl alcohol and diethyl ether and subsequent addition of amiodarone as internal standard hair samples were treated with 500 μl VMA-T M3 buffer reagent for 1 h at 100 °C. After cooling, 10 μl VMA-T M3 extract were injected into chromatographic system. Chromatographic separation was carried out on a reversed phase column using a linear gradient elution with two solvents: 5 mM ammonium formate pH 3.0 (solvent A) and 0.1% formic acid in acetonitrile (solvent B). The flow rate was kept constant at 0.4 ml/min during the analysis. The separated analytes were detected with a triple quadrupole mass spectrometer operated in multiple reaction monitoring mode via positive electrospray ionization. Linear calibration curves were obtained for 11-nor-Δ9-tetrahydrocannabinol-9-carboxylic acid glucuronide with correlation coefficients (r(2)) of 0.99 and a limit of quantification of 0.25 pg/mg hair. Analytical recovery was between 79.6% and 100.7% and intra- and inter-assay imprecision and inaccuracy were always lower than 15%. Ultra-high-pressure liquid chromatography-tandem mass spectrometry analysis of 20 different hair samples of cannabis consumers disclosed the presence of 11-nor-Δ9-tetrahydrocannabinol-9-carboxylic acid glucuronide in the range of 0.5-8.6 pg/mg hair. These data provided a good start to consider 11-nor-Δ9-tetrahydrocannabinol-9-carboxylic acid glucuronide as alternative hair biomarker of cannabis consumption. Copyright © 2015 Elsevier Ireland Ltd. All rights reserved.

“Breakthrough” osmosis and unusually high power densities in Pressure-Retarded Osmosis in non-ideally semi-permeable supported membranes

PubMed Central

Yaroshchuk, Andriy

2017-01-01

Osmosis is the movement of solvent across a membrane induced by a solute-concentration gradient. It is very important for cell biology. Recently, it has started finding technological applications in the emerging processes of Forward Osmosis and Pressure-Retarded Osmosis. They use ultrathin and dense membranes supported mechanically by much thicker porous layers. Until now, these processes have been modelled by assuming the membrane to be ideally-semipermeable. We show theoretically that allowing for even minor deviations from ideal semipermeability to solvent can give rise to a previously overlooked mode of “breakthrough” osmosis. Here the rate of osmosis is very large (compared to the conventional mode) and practically unaffected by the so-called Internal Concentration Polarization. In Pressure-Retarded Osmosis, the power densities can easily exceed the conventional mode by one order of magnitude. Much more robust support layers can be used, which is an important technical advantage (reduced membrane damage) in Pressure-Retarded Osmosis. PMID:28332607

Tuning aggregation of microemulsion droplets and silica nanoparticles using solvent mixtures.

PubMed

Salabat, Alireza; Eastoe, Julian; Mutch, Kevin J; Tabor, Rico F

2008-02-15

The effect of solvent on stability of water-in-oil microemulsions has been studied with AOT (sodium bis(2-ethylhexyl)sulfosuccinate) and different solvent mixtures of n-heptane, toluene and dodecane. Dynamic light scattering DLS was used to monitor the apparent diffusion coefficient D(A) and effective microemulsion droplet diameter on changing composition of the solvent. Interdroplet attractive interactions, as indicated by variations in D(A), can be tuned by formulation of appropriate solvent mixtures using heptane, toluene, and dodecane. In extreme cases, solvent mixtures can be used to induce phase transitions in the microemulsions. Aggregation and stability of model AOT-stabilized silica nanoparticles in different solvents were also investigated to explore further these solvent effects. For both systems the state of aggregation can be correlated with the effective molecular volume of the solvent V(mol)(eff) mixture.

Extraction of Trivalent Actinides and Lanthanides from Californium Campaign Rework Solution Using TODGA-based Solvent Extraction System

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

Benker, Dennis; Delmau, Laetitia Helene; Dryman, Joshua Cory

This report presents the studies carried out to demonstrate the possibility of quantitatively extracting trivalent actinides and lanthanides from highly acidic solutions using a neutral ligand-based solvent extraction system. These studies stemmed from the perceived advantage of such systems over cationexchange- based solvent extraction systems that require an extensive feed adjustment to make a low-acid feed. The targeted feed solutions are highly acidic aqueous phases obtained after the dissolution of curium targets during a californium (Cf) campaign. Results obtained with actual Cf campaign solutions, but highly diluted to be manageable in a glove box, are presented, followed by results ofmore » tests run in the hot cells with Cf campaign rework solutions. It was demonstrated that a solvent extraction system based on the tetraoctyl diglycolamide molecule is capable of quantitatively extracting trivalent actinides from highly acidic solutions. This system was validated using actual feeds from a Cf campaign.« less

The local phase transitions of the solvent in the neighborhood of a solvophobic polymer at high pressures

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

Budkov, Yu. A., E-mail: urabudkov@rambler.ru; National Research University Higher School of Economics, Moscow; Department of Chemistry, Lomonosov Moscow State University, Moscow

2014-11-28

We investigate local phase transitions of the solvent in the neighborhood of a solvophobic polymer chain which is induced by a change of the polymer-solvent repulsion and the solvent pressure in the bulk solution. We describe the polymer in solution by the Edwards model, where the conditional partition function of the polymer chain at a fixed radius of gyration is described by a mean-field theory. The contributions of the polymer-solvent and the solvent-solvent interactions to the total free energy are described within the mean-field approximation. We obtain the total free energy of the solution as a function of the radiusmore » of gyration and the average solvent number density within the gyration volume. The resulting system of coupled equations is solved varying the polymer-solvent repulsion strength at high solvent pressure in the bulk. We show that the coil-globule (globule-coil) transition occurs accompanied by a local solvent evaporation (condensation) within the gyration volume.« less

Evaluation of Solvent Alternatives for Cleaning of Oxygen Systems

NASA Technical Reports Server (NTRS)

Beeson, Harold; Biesinger, Paul; Delgado, Rafael; Antin, Neil

1999-01-01

The NASA White Sands Test Facility (WSTF) in a joint program with the Naval Sea Systems Command has evaluated a number of solvents as alternatives to the use of chlorofluorocarbons currently utilized for cleaning of oxygen systems. Particular attention has been given to the cleaning of gauges and instrumentation used in oxygen service, since there have been no identified aqueous alternatives. The requirements identified as selection criteria, include toxicity, physical properties consistent with application, flammability, oxygen compatibility, and cleaning ability. This paper provides a summary of results and recommendations for solvents evaluated to date.

Gradient Pre-Emphasis to Counteract First-Order Concomitant Fields on Asymmetric MRI Gradient Systems

PubMed Central

Tao, Shengzhen; Weavers, Paul T.; Trzasko, Joshua D.; Shu, Yunhong; Huston, John; Lee, Seung-Kyun; Frigo, Louis M.; Bernstein, Matt A.

2016-01-01

PURPOSE To develop a gradient pre-emphasis scheme that prospectively counteracts the effects of the first-order concomitant fields for any arbitrary gradient waveform played on asymmetric gradient systems, and to demonstrate the effectiveness of this approach using a real-time implementation on a compact gradient system. METHODS After reviewing the first-order concomitant fields that are present on asymmetric gradients, a generalized gradient pre-emphasis model assuming arbitrary gradient waveforms is developed to counteract their effects. A numerically straightforward, simple to implement approximate solution to this pre-emphasis problem is derived, which is compatible with the current hardware infrastructure used on conventional MRI scanners for eddy current compensation. The proposed method was implemented on the gradient driver sub-system, and its real-time use was tested using a series of phantom and in vivo data acquired from 2D Cartesian phase-difference, echo-planar imaging (EPI) and spiral acquisitions. RESULTS The phantom and in vivo results demonstrate that unless accounted for, first-order concomitant fields introduce considerable phase estimation error into the measured data and result in images exhibiting spatially dependent blurring/distortion. The resulting artifacts are effectively prevented using the proposed gradient pre-emphasis. CONCLUSION An efficient and effective gradient pre-emphasis framework is developed to counteract the effects of first-order concomitant fields of asymmetric gradient systems. PMID:27373901

The study of membrane formation via phase inversion method by cloud point and light scattering experiment

NASA Astrophysics Data System (ADS)

Arahman, Nasrul; Maimun, Teuku; Mukramah, Syawaliah

2017-01-01

The composition of polymer solution and the methods of membrane preparation determine the solidification process of membrane. The formation of membrane structure prepared via non-solvent induced phase separation (NIPS) method is mostly determined by phase separation process between polymer, solvent, and non-solvent. This paper discusses the phase separation process of polymer solution containing Polyethersulfone (PES), N-methylpirrolidone (NMP), and surfactant Tetronic 1307 (Tet). Cloud point experiment is conducted to determine the amount of non-solvent needed on induced phase separation. Amount of water required as a non-solvent decreases by the addition of surfactant Tet. Kinetics of phase separation for such system is studied by the light scattering measurement. With the addition of Tet., the delayed phase separation is observed and the structure growth rate decreases. Moreover, the morphology of fabricated membrane from those polymer systems is analyzed by scanning electron microscopy (SEM). The images of both systems show the formation of finger-like macrovoids through the cross-section.

DEMONSTRATION BULLETIN: TERRA KLEEN SOLVENT EXTRACTION TECHNOLOGY - TERRA-KLEEN RESPONSE GROUP, INC.

EPA Science Inventory

The Terra-Kleen Solvent Extraction Technology was developed by Terra-Kleen Response Group, Inc., to remove polychlorinated biphenyls (PCB) and other organic constituents from contaminated soil. This batch process system uses a proprietary solvent at ambient temperatures to treat ...

Superelliptical insert gradient coil with a field-modifying layer for breast imaging.

PubMed

Moon, Sung M; Goodrich, K Craig; Hadley, J Rock; Kim, Seong-Eun; Zeng, Gengsheng L; Morrell, Glen R; McAlpine, Matthew A; Chronik, Blaine A; Parker, Dennis L

2011-03-01

Many MRI applications such as dynamic contrast-enhanced MRI of the breast require high spatial and temporal resolution and can benefit from improved gradient performance, e.g., increased gradient strength and reduced gradient rise time. The improved gradient performance required to achieve high spatial and temporal resolution for this application may be achieved by using local insert gradients specifically designed for a target anatomy. Current flat gradient systems cannot create an imaging volume large enough to accommodate both breasts; further, their gradient fields are not homogeneous, dropping off rapidly with distance from the gradient coil surface. To attain an imaging volume adequate for bilateral breast MRI, a planar local gradient system design has been modified into a superellipse shape, creating homogeneous gradient volumes that are 182% (Gx), 57% (Gy), and 75% (Gz) wider (left/right direction) than those of the corresponding standard planar gradient. Adding an additional field-modifying gradient winding results in an additional improvement of the homogeneous gradient field near the gradient coil surface over the already enlarged homogeneous gradient volumes of the superelliptical gradients (67%, 89%, and 214% for Gx, Gy, and Gz respectively). A prototype y-gradient insert has been built to demonstrate imaging and implementation characteristics of the superellipse gradient in a 3 T MRI system. Copyright © 2010 Wiley-Liss, Inc.

Growth directions of C8-BTBT thin films during drop-casting

NASA Astrophysics Data System (ADS)

Iizuka, Naoki; Zanka, Tomohiko; Onishi, Yosuke; Fujieda, Ichiro

2016-02-01

Because charge transport in a single crystal is anisotropic, control of its orientation is important for enhancing electrical characteristics and reducing variations among devices. For growing an organic thin film, a solution process such as inkjet printing offers advantages in throughput. We have proposed to apply an external temperature gradient during drop-casting and to control the direction of solvent evaporation. In experiment, a temperature gradient was generated in a bare Si substrate by placing it on a Si plate bridging two heat stages. When a solution containing 2,7-dioctyl [1]benzothieno[3,2-b]benzothiophene (C8-BTBT) was dropped on the substrate, evaporation started at the hotter side of the droplet and proceeded toward the colder side. The front line of the liquid was not pinned and the solution extended toward the colder region. As a result, a thin film was formed in a 7mm-long region. The peripheral region of the film was significantly thicker due to the coffee ring effect. The surface of the rest of the film was mostly smooth and terrace structures with 2.6nm steps were observed. The step roughly corresponds to the length of the C8-BTBT molecule. The film thickness varied from 20nm to 50nm over the distance of 3mm. Another film was grown on a glass substrate under a similar condition. Observation of the film with a polarizing microscope revealed that fan-shaped domains were formed in the film and that their optical axes were mostly along the directions of the solvent evaporation.

The macromolecular properties of blood-group-specific glycoproteins. Characterization of a series of fractions obtained by solvent fractionation

PubMed Central

Creeth, J. Michael; Bhaskar, K. Ramakrishnan; Donald, Alastair S. R.; Morgan, Walter T. J.

1974-01-01

1. The glycoprotein components of a human ovarian-cyst fluid were isolated by a solvent [95% (w/w) phenol]-extraction procedure; the phenol-insoluble water-soluble glycoprotein was further fractionated by (NH4)2SO4 and by ethanol to yield eight fractions. 2. The fractions were analysed in terms of amino acids, fucose, galactose, N-acetylglucosamine, N-acetylgalactosamine and sialic acid. Variations occurred, particularly in the proportion of peptide; these were partly correlated with varying extent of serological activity. 3. The fractions were characterized physicochemically in terms of buoyant density and degree of spreading in a density gradient, sedimentation velocity and molecular weight; their partial specific volumes and specific refraction increments were also determined. 4. The fractions showed wide variations in their sedimentation-velocity and density-gradient patterns, and gave evidence of pauci-dispersity in density. The fraction regarded as the most typical blood-group-specific glycoprotein sedimented as a single rapidly spreading peak and was of high molecular weight. 5. Significant correlations were observed between the physical properties of the glycoprotein fractions and the amount of their peptide component. The buoyant densities and sedimentation coefficients varied in a manner that suggested the existence of two families of glycoproteins. 6. It is suggested that variability in the extent of glycosylation, or in the degree of cross-linking, might account for the two families of glycoproteins, and that the extent of cross-linkage might also be a factor determining the solubility of these glycoproteins in hot saturated (NH4)2SO4. ImagesFig. 1.PLATE 1 PMID:4219280

Effects of metals on the transformation of hexabromocyclododecane (HBCD) in solvents: implications for solvent-based recycling of brominated flame retardants.

PubMed

Zhong, Yin; Peng, Ping'an; Yu, Zhiqiang; Deng, Haopeng

2010-09-01

The management of electronic wastes (e-wastes) has become a global issue as it may release large quantities of hazardous materials such as heavy metals and brominated flame retardants (BFRs) to the environment. Solvent-based recycling is a newly developed, efficient and environmentally beneficial technology for the removal or recovery of BFRs from e-wastes. However, little is known about the behavior of BFRs in the solvents and to what extent they may be affected by co-existing heavy metals. This study quantified the rates of transformation of hexabromocyclododecane (HBCD), a widely used BFR, in the presence of different solvents (i.e. acetone, methanol or toluene) and metals (i.e. Ni, Cu, Zn, Fe or Al). Our experimental results showed that less than 20% of HBCD was transformed in all pure solvent systems within 24h at 50 degrees C. The presence of Ni greatly increased the transformation of HBCD (45-99%) in these solvent systems, whereas other metals had little or no effect on extraction process. The kinetics study showed that transformation of HBCD in Ni-containing systems followed pseudo-first-order kinetics and that the highest transformation rate constant (1.2+/-0.1h(-1)) of HBCD was recorded in the Ni+acetone system. The formation of HBr and pentabromocyclododecene in the acetone+Ni system suggested that transformation of HBCD proceeded via dehydrobromination. Collectively, these results indicated that acetone should not be applied in the recycling or extraction of HBCD from Ni-rich e-wastes, as debromination of HBCD may occur during these processes, even at mild extraction temperatures. Copyright (c) 2010 Elsevier Ltd. All rights reserved.

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

NASA Astrophysics Data System (ADS)

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

2018-01-01

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

Spray-on transdermal drug delivery systems.

PubMed

Ibrahim, Sarah A

2015-02-01

Transdermal drug delivery possesses superior advantages over other routes of administration, particularly minimizing first-pass metabolism. Transdermal drug delivery is challenged by the barrier nature of skin. Numerous technologies have been developed to overcome the relatively low skin permeability, including spray-on transdermal systems. A transdermal spray-on system (TSS) usually consists of a solution containing the drug, a volatile solvent and in many cases a chemical penetration enhancer. TSS promotes drug delivery via the complex interplay between solvent evaporation and drug-solvent drag into skin. The volatile solvent carries the drug into the upper layers of the stratum corneum, and as the volatile solvent evaporates, an increase in the thermodynamic activity of the drug occurs resulting in an increased drug loading in skin. TSS is easily applied, delivering flexible drug dosage and associated with lower incidence of skin irritation. TSS provides a fast-drying product where the volatile solvent enables uniform drug distribution with minimal vehicle deposition on skin. TSS ensures precise dose administration that is aesthetically appealing and eliminates concerns of residual drug associated with transdermal patches. Furthermore, it provides a better alternative to traditional transdermal products due to ease of product development and manufacturing.

Oval gradient coils for an open magnetic resonance imaging system with a vertical magnetic field.

PubMed

Matsuzawa, Koki; Abe, Mitsushi; Kose, Katsumi; Terada, Yasuhiko

2017-05-01

Existing open magnetic resonance imaging (MRI) systems use biplanar gradient coils for the spatial encoding of signals. We propose using novel oval gradient coils for an open vertical-field MRI. We designed oval gradients for a 0.3T open MRI system and showed that such a system could outperform a traditional biplanar gradient system while maintaining adequate gradient homogeneity and subject accessibility. Such oval gradient coils would exhibit high efficiency, low inductance and resistance, and high switching capability. Although the designed oval Y and Z coils showed more heat dissipation and less cooling capability than biplanar coils with the same gap, they showed an efficient heat-dissipation path to the surrounding air, which would alleviate the heat problem. The performance of the designed oval-coil system was demonstrated experimentally by imaging a human hand. Copyright © 2017 Elsevier Inc. All rights reserved.

Water-compatible molecularly imprinted polymers for efficient direct injection on-line solid-phase extraction of ropivacaine and bupivacaine from human plasma.

PubMed

Cobb, Zoe; Sellergren, Börje; Andersson, Lars I

2007-12-01

Two novel molecularly imprinted polymers (MIPs) selected from a combinatorial library of bupivacaine imprinted polymers were used for selective on-line solid-phase extraction of bupivacaine and ropivacaine from human plasma. The MIPs were prepared using methacrylic acid as the functional monomer, ethylene glycol dimethacrylate as the cross-linking monomer and in addition hydroxyethylmethacrylate to render the polymer surface hydrophilic. The novel MIPs showed high selectivity for the analytes and required fewer and lower concentrations of additives to suppress non-specific adsorption compared with a conventional MIP. This enabled the development of an on-line system for direct extraction of buffered plasma. Selective extraction was achieved without the use of time-consuming solvent switch steps, and transfer of the analytes from the MIP column to the analytical column was carried out under aqueous conditions fully compatible with reversed-phase LC gradient separation of analyte and internal standard. The MIPs showed excellent aqueous compatibility and yielded extractions with acceptable recovery and high selectivity.

New phenolic grape skin products from Vitis vinifera cv. Pinot Noir.

PubMed

Kneknopoulos, Petros; Skouroumounis, George K; Hayasaka, Yoji; Taylor, Dennis K

2011-02-09

Anthocyanins and their related compounds were extracted from grape skins of Pinot noir, using 50% aqueous methanol, and purified by solid phase extraction chromatography using XAD-7 resin to obtain a pigment-rich fraction. This fraction was subjected to multilayer coil countercurrent chromatography (MLCCC) using a quaternary solvent system consisting of tert-butyl methyl ether/n-butanol/acetonitrile/water acidified with 0.01% trifluoroacetic acid (2:2:0.1-1.8:5) (v/v/v/v) in a step gradient elution to separate anthocyanin oligomers from grape anthocyanins. In the process of the characterization of the MLCCC fractions by electrospray mass spectrometry, two noncolored anthocyanin derivatives were found and characterized on the basis of their mass spectral data. As a result, these compounds have been tentatively identified as coupling products between both hydrated malvidin-3-glucoside and peonidin-3-glucoside, with 2-S-glutathionyl caffeoyl tartaric acid (GRP). It is therefore proposed that grape skins contain this new class of coupling product, and a possible chemical pathway for their formation is suggested.

Separation of polyphenols and caffeine from the acetone extract of fermented tea leaves (Camellia sinensis) using high-performance countercurrent chromatography.

PubMed

Choi, Soo Jung; Hong, Yong Deog; Lee, Bumjin; Park, Jun Seong; Jeong, Hyun Woo; Kim, Wan Gi; Shin, Song Seok; Yoon, Kee Dong

2015-07-21

Leaves from Camellia sienensis are a popular natural source of various beverage worldwide, and contain caffeine and polyphenols derived from catechin analogues. In the current study, caffeine (CAF, 1) and three tea polyphenols including (-)-epigallocatechin 3-O-gallate (EGCg, 2), (-)-gallocatechin 3-O-gallate (GCg, 3), and (-)-epicatechin 3-O-gallate (ECg, 4) were isolated and purified by flow-rate gradient high-performance countercurrent chromatography (HPCCC) using a two-phase solvent system composed of n-hexane-ethyl acetate-methanol-water (1:9:1:9, v/v). Two hundred milligrams of acetone-soluble extract from fermented C. sinensis leaves was separated by HPCCC to give 1 (25.4 mg), 2 (16.3 mg), 3 (11.1 mg) and 4 (4.4 mg) with purities over 98%. The structures of 1-4 were elucidated by QTOF-MS, as well as 1H- and 13C-NMR, and the obtained data were compared to the previously reported values.

Linear-scaling time-dependent density-functional theory beyond the Tamm-Dancoff approximation: Obtaining efficiency and accuracy with in situ optimised local orbitals

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

Zuehlsdorff, T. J., E-mail: tjz21@cam.ac.uk; Payne, M. C.; Hine, N. D. M.

2015-11-28

We present a solution of the full time-dependent density-functional theory (TDDFT) eigenvalue equation in the linear response formalism exhibiting a linear-scaling computational complexity with system size, without relying on the simplifying Tamm-Dancoff approximation (TDA). The implementation relies on representing the occupied and unoccupied subspaces with two different sets of in situ optimised localised functions, yielding a very compact and efficient representation of the transition density matrix of the excitation with the accuracy associated with a systematic basis set. The TDDFT eigenvalue equation is solved using a preconditioned conjugate gradient algorithm that is very memory-efficient. The algorithm is validated on amore » small test molecule and a good agreement with results obtained from standard quantum chemistry packages is found, with the preconditioner yielding a significant improvement in convergence rates. The method developed in this work is then used to reproduce experimental results of the absorption spectrum of bacteriochlorophyll in an organic solvent, where it is demonstrated that the TDA fails to reproduce the main features of the low energy spectrum, while the full TDDFT equation yields results in good qualitative agreement with experimental data. Furthermore, the need for explicitly including parts of the solvent into the TDDFT calculations is highlighted, making the treatment of large system sizes necessary that are well within reach of the capabilities of the algorithm introduced here. Finally, the linear-scaling properties of the algorithm are demonstrated by computing the lowest excitation energy of bacteriochlorophyll in solution. The largest systems considered in this work are of the same order of magnitude as a variety of widely studied pigment-protein complexes, opening up the possibility of studying their properties without having to resort to any semiclassical approximations to parts of the protein environment.« less

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

PubMed

Corrigan, Owen I; Crean, Abina M

2002-10-01

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

Computational study of the free energy landscape of the miniprotein CLN025 in explicit and implicit solvent.

PubMed

Rodriguez, Alex; Mokoema, Pol; Corcho, Francesc; Bisetty, Khrisna; Perez, Juan J

2011-02-17

The prediction capabilities of atomistic simulations of peptides are hampered by different difficulties, including the reliability of force fields, the treatment of the solvent or the adequate sampling of the conformational space. In this work, we have studied the conformational profile of the 10 residue miniprotein CLN025 known to exhibit a β-hairpin in its native state to understand the limitations of implicit methods to describe solvent effects and how these may be compensated by using different force fields. For this purpose, we carried out a thorough sampling of the conformational space of CLN025 in explicit solvent using the replica exchange molecular dynamics method as a sampling technique and compared the results with simulations of the system modeled using the analytical linearized Poisson-Boltzmann (ALPB) method with three different AMBER force fields: parm94, parm96, and parm99SB. The results show the peptide to exhibit a funnel-like free energy landscape with two minima in explicit solvent. In contrast, the higher minimum nearly disappears from the energy surface when the system is studied with an implicit representation of the solvent. Moreover, the different force fields used in combination with the ALPB method do not describe the system in the same manner. The results of this work suggest that the balance between intra- and intermolecular interactions is the cause of the differences between implicit and explicit solvent simulations in this system, stressing the role of the environment to define properly the conformational profile of a peptide in solution.

Computer simulation of the linear and nonlinear optical susceptibilities of p-nitroaniline in cyclohexane, 1,4-dioxane, and tetrahydrofuran in quadrupolar approximation. II. Local field effects and optical susceptibilitities.

PubMed

Reis, H; Papadopoulos, M G; Grzybowski, A

2006-09-21

This is the second part of a study to elucidate the local field effects on the nonlinear optical properties of p-nitroaniline (pNA) in three solvents of different multipolar character, that is, cyclohexane (CH), 1,4-dioxane (DI), and tetrahydrofuran (THF), employing a discrete description of the solutions. By the use of liquid structure information from molecular dynamics simulations and molecular properties computed by high-level ab initio methods, the local field and local field gradients on p-nitroaniline and the solvent molecules are computed in quadrupolar approximation. To validate the simulations and the induction model, static and dynamic (non)linear properties of the pure solvents are also computed. With the exception of the static dielectric constant of pure THF, a good agreement between computed and experimental refractive indices, dielectric constants, and third harmonic generation signals is obtained for the solvents. For the solutions, it is found that multipole moments up to two orders higher than quadrupole have a negligible influence on the local fields on pNA, if a simple distribution model is employed for the electric properties of pNA. Quadrupole effects are found to be nonnegligible in all three solvents but are especially pronounced in the 1,4-dioxane solvent, in which the local fields are similar to those in THF, although the dielectric constant of DI is 2.2 and that of the simulated THF is 5.4. The electric-field-induced second harmonic generation (EFISH) signal and the hyper-Rayleigh scattering signal of pNA in the solutions computed with the local field are in good to fair agreement with available experimental results. This confirms the effect of the "dioxane anomaly" also on nonlinear optical properties. Predictions based on an ellipsoidal Onsager model as applied by experimentalists are in very good agreement with the discrete model predictions. This is in contrast to a recent discrete reaction field calculation of pNA in 1,4-dioxane, which found that the predicted first hyperpolarizability of pNA deviated strongly from the predictions obtained using Onsager-Lorentz local field factors.

PERTURBATION OF VOLTAGE-SENSITIVE CALCIUM FUNCTION IN PHEOCHROMOCYTOMA CELLS BY VOLATILE ORGANIC SOLVENTS.

EPA Science Inventory

Volatile organic solvents such as toluene (TOL) and trichloroethylene perturb nervous system function and share characteristic effects with other central nervous system depressants such as anesthetic gasses, ethanol, benzodiazepines and barbiturates. Recently, mechanistic studies...

Nonisothermal Brownian motion: Thermophoresis as the macroscopic manifestation of thermally biased molecular motion.

PubMed

Brenner, Howard

2005-12-01

A quiescent single-component gravity-free gas subject to a small steady uniform temperature gradient T, despite being at rest, is shown to experience a drift velocity UD=-D* gradient ln T, where D* is the gas's nonisothermal self-diffusion coefficient. D* is identified as being the gas's thermometric diffusivity alpha. The latter differs from the gas's isothermal isotopic self-diffusion coefficient D, albeit only slightly. Two independent derivations are given of this drift velocity formula, one kinematical and the other dynamical, both derivations being strictly macroscopic in nature. Within modest experimental and theoretical uncertainties, this virtual drift velocity UD=-alpha gradient ln T is shown to be constitutively and phenomenologically indistinguishable from the well-known experimental and theoretical formulas for the thermophoretic velocity U of a macroscopic (i.e., non-Brownian) non-heat-conducting particle moving under the influence of a uniform temperature gradient through an otherwise quiescent single-component rarefied gas continuum at small Knudsen numbers. Coupled with the size independence of the particle's thermophoretic velocity, the empirically observed equality, U=UD, leads naturally to the hypothesis that these two velocities, the former real and the latter virtual, are, in fact, simply manifestations of the same underlying molecular phenomenon, namely the gas's Brownian movement, albeit biased by the temperature gradient. This purely hydrodynamic continuum-mechanical equality is confirmed by theoretical calculations effected at the kinetic-molecular level on the basis of an existing solution of the Boltzmann equation for a quasi-Lorentzian gas, modulo small uncertainties pertaining to the choice of collision model. Explicitly, this asymptotically valid molecular model allows the virtual drift velocity UD of the light gas and the thermophoretic velocity U of the massive, effectively non-Brownian, particle, now regarded as the tracer particle of the light gas's drift velocity, to each be identified with the Chapman-Enskog "thermal diffusion velocity" of the quasi-Lorentzian gas, here designated by the symbol UM/M, as calculated by de la Mora and Mercer. It is further pointed out that, modulo the collective uncertainties cited above, the common velocities UD,U, and UM/M are identical to the single-component gas's diffuse volume current jv, the latter representing yet another, independent, strictly continuum-mechanical concept. Finally, comments are offered on the extension of the single-component drift velocity notion to liquids, and its application towards rationalizing Soret thermal-diffusion separation phenomena in quasi-Lorentzian liquid-phase binary mixtures composed of disparately sized solute and solvent molecules, with the massive Brownian solute molecules (e.g., colloidal particles) present in disproportionately small amounts relative to that of the solvent.

Performance of thermally-chargeable supercapacitors in different solvents.

PubMed

Lim, Hyuck; Zhao, Cang; Qiao, Yu

2014-07-07

The influence of solvent on the temperature sensitivity of the electrode potential of thermally-chargeable supercapacitors (TCSs) is investigated. For large electrodes, the output voltage is positively correlated with the dielectric constant of solvent. When nanoporous carbon electrodes are used, different characteristics of system performance are observed, suggesting that possible size effects must be taken into consideration when the solvent molecules and solvated ions are confined in a nanoenvironment.

Rapid separation and identification of anthocyanins from flowers of Viola yedoensis and V. prionantha by high-performance liquid chromatography-photodiode array detection-electrospray ionisation mass spectrometry.

PubMed

Zhang, Jie; Wang, Liang-Sheng; Gao, Jin-Ming; Xu, Yan-Jun; Li, Lian-Fang; Li, Chong-Hui

2012-01-01

Anthocyanins are important plant secondary metabolites. They show strong antioxidant activities and have potential as anti-cancer agents. Viola yedoensis and V. prionantha are traditional Chinese medicines and ornamental plants. However, the anthocyanin compositions of these two species are still unresolved. To develop a rapid and reliable high-performance liquid chromatography (HPLC) method for the separation and identification of anthocyanins from V. yedoensis and V. prionantha. Samples were extracted in methanol-water-formic acid-TFA (70:27:2:1, v/v). HPLC analysis was done on a C(18) column (TSK-GEL ODS-80Ts: 150 × 4.6 mm i.d.). Four solvent systems were tested to optimise the separation of anthocyanins using different gradient separation systems. HPLC-photodiode array detection (DAD) coupled to electrospray ionisation mass spectrometry (ESI-MS) was used to carry out the comprehensive characterisation of anthocyanins. Fourteen anthocyanins were characterised within 40 min with satisfactory peak resolution by a gradient composed of 10% aqueous formic acid and formic acid-acetonitrile-water (10:40:50, v/v). The calibration curve showed an excellent linear regression (r(2)  = 0.9995) and low intra- and inter-day variations (RSD < 3.67%). The detected anthocyanins derived from Dp, Cy, Pt, Mv and Pn, could be divided into three groups: non-acylated glycosides, acetylglycosides and coumaroylglycosides. Anthocyanins distribution exhibited remarkable differences in aglycone levels and acylation patterns. The optimised method was successfully applied for the analysis of 14 anthocyanins from V. yedoensis and V. prionantha. The identification of anthocyanin constitutions is valuable for breeding and will open up new prospects for their medicinal application. Copyright © 2011 John Wiley & Sons, Ltd.

Occupational solvent exposure and adult chronic lymphocytic leukemia: No risk in a population-based case-control study in four Nordic countries.

PubMed

Talibov, Madar; Auvinen, Anssi; Weiderpass, Elisabete; Hansen, Johnni; Martinsen, Jan-Ivar; Kjaerheim, Kristina; Tryggvadottir, Laufey; Pukkala, Eero

2017-09-15

The aim of this study was to assess the effect of occupational solvent exposure on the risk of adult chronic lymphocytic leukemia (CLL). The current case-control study was nested in the Nordic Occupational Cancer Study (NOCCA) cohort. 20,615 CLL cases diagnosed in 1961-2005 in Finland, Iceland, Norway, and Sweden, and 103,075 population-based controls matched by year of birth, sex, and country were included. Occupational histories for cases and controls were obtained from census records in 1960, 1970, 1980/1981, and 1990. Exposure to selected solvents was estimated by using the NOCCA job-exposure matrix (NOCCA-JEM). Odds ratios (OR) and 95% confidence intervals (95% CI) were estimated by using conditional logistic regression models. Overall, nonsignificant CLL risk elevations were observed for methylene chloride, perchloroethylene, and 1,1,1-trichloroethane. Compared to unexposed, significantly increased risks were observed for cumulative perchloroethylene exposure ≤13.3 ppm-years (OR = 1.85, 95% CI 1.16-2.96) and average life-time perchloroethylene exposure ≤2.5 ppm (1.61, 95% CI 1.01-2.56) among women, and cumulative methylene chloride exposure ≤12.5 ppm-years (OR = 1.19, 95% CI 1.01-1.41) and 12.5-74.8 ppm-years (OR = 1.23, 95% CI 1.01-1.51) among men in an analysis with 5 years lag-time, though without dose-response pattern. Decreased CLL risk was observed for aliphatic and alicyclic hydrocarbon solvents and toluene. This study did not support associations for solvent exposure and CLL. Observed weak associations for methylene chloride, perchloroethylene, 1,1,1-trichloroethane exposures, aliphatic and alicyclic hydrocarbons and toluene were not consistent across sexes, and showed no gradient with amount of exposure. © 2017 UICC.

Mortality and cancer incidence of aircraft maintenance workers exposed to trichloroethylene and other organic solvents and chemicals: extended follow up

PubMed Central

Blair, A.; Hartge, P.; Stewart, P. A.; McAdams, M.; Lubin, J.

1998-01-01

OBJECTIVES: To extend the follow up of a cohort of 14,457 aircraft maintenance workers to the end of 1990 to evaluate cancer risks from potential exposure to trichloroethylene and other chemicals. METHODS: The cohort comprised civilians employed for at least one year between 1952 and 1956, of whom 5727 had died by 31 December 1990. Analyses compared the mortality of the cohort with the general population of Utah and the mortality and cancer incidence of exposed workers with those unexposed to chemicals, while adjusting for age, sex and calendar time. RESULTS: In the combined follow up period (1952-90), mortality from all causes and all cancer was close to expected (standardised mortality ratios (SMRs) 97 and 96, respectively). Significant excesses occurred for ischaemic heart disease (SMR 108), asthma (SMR 160), and cancer of the bone (SMR 227), whereas significant deficits occurred for cerebrovascular disease (SMR 88), accidents (SMR 70), and cancer of the central nervous system (SMR 64). Workers exposed to trichloroethylene showed non-significant excesses for non-Hodgkin's lymphoma (relative risk (RR) 2.0), and cancers of the oesophagus (RR 5.6), colon (RR 1.4), primary liver (RR 1.7), breast (RR 1.8), cervix (RR 1.8), kidney (RR 1.6), and bone (RR 2.1). None of these cancers showed an exposure- response gradient and RRs among workers exposed to other chemicals but not trichloroethylene often had RRs as large as workers exposed to trichloroethylene. Workers exposed to solvents other than trichloroethylene had slightly increased mortality from asthma, non- Hodgkin's lymphoma, multiple myeloma, and breast cancer. CONCLUSION: These findings do not strongly support a causal link with trichloroethylene because the associations were not significant, not clearly dose-related, and inconsistent between men and women. Because findings from experimental investigations and other epidemiological studies on solvents other than trichloroethylene provide some biological plausibility, the suggested links between these chemicals and non-Hodgkin's lymphoma, multiple myeloma, and breast cancer found here deserve further attention. Although this extended follow up cannot rule out a connection between exposures to solvents and some diseases, it seems clear that these workers have not experienced a major increase in cancer mortality or cancer incidence.   PMID:9624267

Centrifugal partition chromatography: A preparative tool for isolation and purification of xylindein from Chlorociboria aeruginosa.

PubMed

Boonloed, Anukul; Weber, Genevieve L; Ramzy, Kelly M; Dias, Veronica R; Remcho, Vincent T

2016-12-23

A centrifugal partition chromatography (CPC) method was developed for the preparative-scale isolation and purification of xylindein from the wood-staining fungi, Chlorociboria aeruginosa. Xylindein, a blue-green pigment naturally secreted from the hyphae and fruiting bodies of the fungus, has great value in the decorative wood industry and textile coloration. Xylindein has great potential for use as a fluorescent labeling agent as well as in organic semiconductor applications. However, a primary limitation of xylindein is its poor solubility in most common HPLC solvents. Consequently, it is arduous to purify using preparative liquid chromatography or solid-phase extraction (SPE). Support-free, liquid-liquid chromatographic methods, including CPC, where solutes are separated based on their different distribution coefficients (K D ) between two immiscible solvent systems, are promising alternatives for the purification of the compound on a preparative scale. In this work, a new biphasic solvent system suitable for CPC separation of xylindein was developed. Various groups of solvents were assessed for their suitability as xylindein extractants. A new solvent system suitable for CPC separation of xylindein, composed of heptane/THF/MEK/acetonitrile/acetic acid/water, was developed. This solvent system yielded a K D value for xylindein of 1.54±0.04, as determined by HPLC (n=3). The compositions of the upper phase and lower phase of the solvent system were determined by Heteronuclear Single Quantum Correlation (HSQC) NMR and proton NMR. A CPC system, equipped with a fraction collector, was used for the isolation of xylindein from crude extracts. The xylindein fractions isolated by the CPC were then analyzed using HPLC and presented as a fractogram. Based on the CPC fractogram, the purified xylindein fractions were achieved after 30min CPC separation time, yielding 71% extraction efficiency. The developed CPC method allowed for isolation of this naturally sourced xylindein in amounts suitable for further study. Copyright © 2016 Elsevier B.V. All rights reserved.

Gelcasting compositions having improved drying characteristics and machinability

DOEpatents

Janney, Mark A.; Walls, Claudia A. H.

2001-01-01

A gelcasting composition has improved drying behavior, machinability and shelf life in the dried and unfired state. The composition includes an inorganic powder, solvent, monomer system soluble in the solvent, an initiator system for polymerizing the monomer system, and a plasticizer soluble in the solvent. Dispersants and other processing aides to control slurry properties can be added. The plasticizer imparts an ability to dry thick section parts, to store samples in the dried state without cracking under conditions of varying relative humidity, and to machine dry gelcast parts without cracking or chipping. A method of making gelcast parts is also disclosed.

Comparison of twin-cell centrifugal partition chromatographic columns with different cell volume.

PubMed

Goll, Johannes; Audo, Gregoire; Minceva, Mirjana

2015-08-07

Two twin-cell centrifugal partition chromatographic columns (SCPC 250 and SCPE-250-BIO, Armen Instrument, France) with the same column volume but different cell size and number were compared in terms of stationary phase retention and column efficiency. The columns were tested with two types of solvent systems: a commonly used organic solvent based biphasic system from the ARIZONA solvent system family and a polymer/salt based aqueous two phase system (ATPS). The efficiency of the columns was evaluated by pulse injection experiments of two benzenediols (pyrocatechol and hydroquinone) in the case of the ARIZONA system and a protein mixture (myoglobin and lysozyme) in the case of the ATPS. As result of high stationary phase retention, the column with the lower number of larger twin-cells (SCPE-250-BIO) is suitable for protein separations using ATPS. On the other hand, due to higher column efficiency, the column with the greater number of smaller cells (SCPC 250) is superior for batch elution separations performed with standard liquid-liquid chromatography organic solvent based biphasic systems. Copyright © 2015 Elsevier B.V. All rights reserved.

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

PubMed

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

2013-09-28

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

UV-Vis spectroscopic study and DFT calculation on the solvent effect of trimethoprim in neat solvents and aqueous mixtures.

PubMed

Almandoz, M C; Sancho, M I; Duchowicz, P R; Blanco, S E

2014-08-14

The solvatochromic behavior of trimethoprim (TMP) was analyzed using UV-Vis spectroscopy and DFT methods in neat and binary aqueous solvent mixtures. The effects of solvent dipolarity/polarizability and solvent-solute hydrogen bonding interactions on the absorption maxima were evaluated by means of the linear solvation energy relationship concept of Kamlet and Taft. This analysis indicated that both interactions play an important role in the position of the absorption maxima in neat solvents. The simulated absorption spectra of TMP and TMP:(solvent)n complexes in ACN and H2O using TD-DFT methods were in agreement with the experimental ones. Binary aqueous mixtures containing as co-solvents DMSO, ACN and EtOH were studied. Preferential solvation was detected as a nonideal behavior of the wavenumber curve respective to the analytical mole fraction of co-solvent in all binary systems. TMP molecules were preferentially solvated by the organic solvent over the whole composition range. Index of preferential solvation, as well as the influence of solvent parameters were calculated as a function of solvent composition. Copyright © 2014 Elsevier B.V. All rights reserved.

Supersonic gas-liquid cleaning system

NASA Technical Reports Server (NTRS)

Caimi, Raoul E. B.; Thaxton, Eric A.

1994-01-01

A system to perform cleaning and cleanliness verification is being developed to replace solvent flush methods using CFC 113 for fluid system components. The system is designed for two purposes: internal and external cleaning and verification. External cleaning is performed with the nozzle mounted at the end of a wand similar to a conventional pressure washer. Internal cleaning is performed with a variety of fixtures designed for specific applications. Internal cleaning includes tubes, pipes, flex hoses, and active fluid components such as valves and regulators. The system uses gas-liquid supersonic nozzles to generate high impingement velocities at the surface of the object to be cleaned. Compressed air or any inert gas may be used to provide the conveying medium for the liquid. The converging-diverging nozzles accelerate the gas-liquid mixture to supersonic velocities. The liquid being accelerated may be any solvent including water. This system may be used commercially to replace CFC and other solvent cleaning methods widely used to remove dust, dirt, flux, and lubricants. In addition, cleanliness verification can be performed without the solvents which are typically involved. This paper will present the technical details of the system, the results achieved during testing at KSC, and future applications for this system.

Supersonic gas-liquid cleaning system

NASA Astrophysics Data System (ADS)

Caimi, Raoul E. B.; Thaxton, Eric A.

1994-02-01

A system to perform cleaning and cleanliness verification is being developed to replace solvent flush methods using CFC 113 for fluid system components. The system is designed for two purposes: internal and external cleaning and verification. External cleaning is performed with the nozzle mounted at the end of a wand similar to a conventional pressure washer. Internal cleaning is performed with a variety of fixtures designed for specific applications. Internal cleaning includes tubes, pipes, flex hoses, and active fluid components such as valves and regulators. The system uses gas-liquid supersonic nozzles to generate high impingement velocities at the surface of the object to be cleaned. Compressed air or any inert gas may be used to provide the conveying medium for the liquid. The converging-diverging nozzles accelerate the gas-liquid mixture to supersonic velocities. The liquid being accelerated may be any solvent including water. This system may be used commercially to replace CFC and other solvent cleaning methods widely used to remove dust, dirt, flux, and lubricants. In addition, cleanliness verification can be performed without the solvents which are typically involved. This paper will present the technical details of the system, the results achieved during testing at KSC, and future applications for this system.

Retention prediction of highly polar ionizable solutes under gradient conditions on a mixed-mode reversed-phase and weak anion-exchange stationary phase.

PubMed

Balkatzopoulou, P; Fasoula, S; Gika, H; Nikitas, P; Pappa-Louisi, A

2015-05-29

In the present work the retention of three highly polar and ionizable solutes - uric acid, nicotinic acid and ascorbic acid - was investigated on a mixed-mode reversed-phase and weak anion-exchange (RP/WAX) stationary phase in buffered aqueous acetonitrile (ACN) mobile phases. A U-shaped retention behavior was observed for all solutes with respect to the eluent organic modifier content studied in a range of 5-95% (v/v). This retention behavior clearly demonstrates the presence of a HILIC-type retention mechanism at ACN-rich hydro-organic eluents and an RP-like retention at aqueous-rich hydro-organic eluents. Hence, this column should be promising for application under both RP and HILIC gradient elution modes. For this reason, a series of programmed elution runs were carried out with increasing (RP) and decreasing (HILIC) organic solvent concentration in the mobile phase. This dual gradient process was successfully modeled by two retention models exhibiting a quadratic or a cubic dependence of the logarithm of the solute retention factor (lnk) upon the organic modifier volume fraction (φ). It was found that both models produced by gradient retention data allow the prediction of solute retention times for both types of programmed elution on the mixed-mode column. Four, in the case of the quadratic model, or five, in the case of the cubic model, initial HILIC- and RP-type gradient runs gave satisfactory retention predictions of any similar kind elution program, even with different flow rate, with an overall error of only 2.5 or 1.7%, respectively. Copyright © 2015 Elsevier B.V. All rights reserved.

Free Energy, Enthalpy and Entropy from Implicit Solvent End-Point Simulations.

PubMed

Fogolari, Federico; Corazza, Alessandra; Esposito, Gennaro

2018-01-01

Free energy is the key quantity to describe the thermodynamics of biological systems. In this perspective we consider the calculation of free energy, enthalpy and entropy from end-point molecular dynamics simulations. Since the enthalpy may be calculated as the ensemble average over equilibrated simulation snapshots the difficulties related to free energy calculation are ultimately related to the calculation of the entropy of the system and in particular of the solvent entropy. In the last two decades implicit solvent models have been used to circumvent the problem and to take into account solvent entropy implicitly in the solvation terms. More recently outstanding advancement in both implicit solvent models and in entropy calculations are making the goal of free energy estimation from end-point simulations more feasible than ever before. We review briefly the basic theory and discuss the advancements in light of practical applications.

A multi target approach to control chemical reactions in their inhomogeneous solvent environment

NASA Astrophysics Data System (ADS)

Keefer, Daniel; Thallmair, Sebastian; Zauleck, Julius P. P.; de Vivie-Riedle, Regina

2015-12-01

Shaped laser pulses offer a powerful tool to manipulate molecular quantum systems. Their application to chemical reactions in solution is a promising concept to redesign chemical synthesis. Along this road, theoretical developments to include the solvent surrounding are necessary. An appropriate theoretical treatment is helpful to understand the underlying mechanisms. In our approach we simulate the solvent by randomly selected snapshots from molecular dynamics trajectories. We use multi target optimal control theory to optimize pulses for the various arrangements of explicit solvent molecules simultaneously. This constitutes a major challenge for the control algorithm, as the solvent configurations introduce a large inhomogeneity to the potential surfaces. We investigate how the algorithm handles the new challenges and how well the controllability of the system is preserved with increasing complexity. Additionally, we introduce a way to statistically estimate the efficiency of the optimized laser pulses in the complete thermodynamical ensemble.

Effect of extraction method on the yield of furanocoumarins from fruits of Archangelica officinalis Hoffm.

PubMed

Waksmundzka-Hajnos, M; Petruczynik, A; Dragan, A; Wianowska, D; Dawidowicz, A L

2004-01-01

Optimal conditions for the extraction and analysis of furanocoumarins from fruits of Archangelica officinalis Hoffm. have been determined. The following extraction methods were used: exhaustive extraction in a Soxhlet apparatus, ultrasonication at 25 and 60 degrees C, microwave-assisted solvent extraction in open and closed systems, and accelerated solvent extraction (ASE). In most cases the yields of furanocoumarins were highest using the ASE method. The effects of extracting solvent, temperature and time of extraction using this method were investigated. The highest yield of furanocoumarins by ASE was obtained with methanol at 100-130 degrees C for 10 min. The extraction yields of furanocoumarins from plant material by ultrasonication at 60 degrees C and microwave-assisted solvent extraction in an open system were comparable to the extraction yields obtained in the time- and solvent-consuming exhaustive process involving the Soxhlet apparatus.

Functional Sites Induce Long-Range Evolutionary Constraints in Enzymes

PubMed Central

Jack, Benjamin R.; Meyer, Austin G.; Echave, Julian; Wilke, Claus O.

2016-01-01

Functional residues in proteins tend to be highly conserved over evolutionary time. However, to what extent functional sites impose evolutionary constraints on nearby or even more distant residues is not known. Here, we report pervasive conservation gradients toward catalytic residues in a dataset of 524 distinct enzymes: evolutionary conservation decreases approximately linearly with increasing distance to the nearest catalytic residue in the protein structure. This trend encompasses, on average, 80% of the residues in any enzyme, and it is independent of known structural constraints on protein evolution such as residue packing or solvent accessibility. Further, the trend exists in both monomeric and multimeric enzymes and irrespective of enzyme size and/or location of the active site in the enzyme structure. By contrast, sites in protein–protein interfaces, unlike catalytic residues, are only weakly conserved and induce only minor rate gradients. In aggregate, these observations show that functional sites, and in particular catalytic residues, induce long-range evolutionary constraints in enzymes. PMID:27138088

Elucidation of ionic interactions in the protic ionic liquid solutions by isothermal titration calorimetry.

PubMed

Rai, Gitanjali; Kumar, Anil

2014-04-17

The strong hydrogen-bonded network noted in protic ionic liquids (PILs) may lead to stronger interactions of the ionic entities of PILs with solvents (water, methanol, ethylene glycol, dimethylsulfoxide (DMSO), N,N'-dimethylformamide (DMF)) as compared with those of aprotic ionic liquids (APILs). The PILs used in this work are 1-methylimidazolium tetrafluoroborate, 2-methylpyridinium tetrafluoroborate, and N-methylpyrrolodinium tetrafluoroborate in comparison to 1-butyl-3-methylimidazolium tetrafluoroborate, which is classified as an APIL. In this work, the excess partial molar enthalpy, H(E)IL obtained from isothermal calorimetric titrations at 298.15 K is used to probe the nature of interactions of the PIL cations with solvent molecules against those present in APIL-solvent systems. This work also reports interesting flip-flopping in the thermal behavior of these PIL-solvent systems depending upon the structure of the cationic ring of a PIL. In some cases, these flip-flops are the specific fingerprints for specific PILs in a common solvent environment. The excess partial molar enthalpy at infinite dilution, H(E,∞)IL, of these PILs bears a critical dependence on the solvent properties. An analysis of relative apparent molar enthalpies, ϕL, of the PIL solutions by the ion interaction model of Pitzer yields important information on ionic interactions of these systems.

Investigation of Cleanliness Verification Techniques for Rocket Engine Hardware

NASA Technical Reports Server (NTRS)

Fritzemeier, Marilyn L.; Skowronski, Raymund P.

1994-01-01

Oxidizer propellant systems for liquid-fueled rocket engines must meet stringent cleanliness requirements for particulate and nonvolatile residue. These requirements were established to limit residual contaminants which could block small orifices or ignite in the oxidizer system during engine operation. Limiting organic residues in high pressure oxygen systems, such as in the Space Shuttle Main Engine (SSME), is particularly important. The current method of cleanliness verification for the SSME uses an organic solvent flush of the critical hardware surfaces. The solvent is filtered and analyzed for particulate matter followed by gravimetric determination of the nonvolatile residue (NVR) content of the filtered solvent. The organic solvents currently specified for use (1, 1, 1-trichloroethane and CFC-113) are ozone-depleting chemicals slated for elimination by December 1995. A test program is in progress to evaluate alternative methods for cleanliness verification that do not require the use of ozone-depleting chemicals and that minimize or eliminate the use of solvents regulated as hazardous air pollutants or smog precursors. Initial results from the laboratory test program to evaluate aqueous-based methods and organic solvent flush methods for NVR verification are provided and compared with results obtained using the current method. Evaluation of the alternative methods was conducted using a range of contaminants encountered in the manufacture of rocket engine hardware.

Systems and methods for laser assisted sample transfer to solution for chemical analysis

DOEpatents

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

2014-06-03

Systems and methods are described for laser ablation of an analyte from a specimen and capturing of the analyte in a dispensed solvent to form a testing solution. A solvent dispensing and extraction system can form a liquid microjunction with the specimen. The solvent dispensing and extraction system can include a surface sampling probe. The laser beam can be directed through the surface sampling probe. The surface sampling probe can also serve as an atomic force microscopy probe. The surface sampling probe can form a seal with the specimen. The testing solution including the analyte can then be analyzed using an analytical instrument or undergo further processing.

Systems and methods for laser assisted sample transfer to solution for chemical analysis

DOEpatents

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

2015-09-29

Systems and methods are described for laser ablation of an analyte from a specimen and capturing of the analyte in a dispensed solvent to form a testing solution. A solvent dispensing and extraction system can form a liquid microjunction with the specimen. The solvent dispensing and extraction system can include a surface sampling probe. The laser beam can be directed through the surface sampling probe. The surface sampling probe can also serve as an atomic force microscopy probe. The surface sampling probe can form a seal with the specimen. The testing solution including the analyte can then be analyzed using an analytical instrument or undergo further processing.

Systems and methods for laser assisted sample transfer to solution for chemical analysis

DOEpatents

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

2013-08-27

Systems and methods are described for laser ablation of an analyte from a specimen and capturing of the analyte in a dispensed solvent to form a testing solution. A solvent dispensing and extraction system can form a liquid microjunction with the specimen. The solvent dispensing and extraction system can include a surface sampling probe. The laser beam can be directed through the surface sampling probe. The surface sampling probe can also serve as an atomic force microscopy probe. The surface sampling probe can form a seal with the specimen. The testing solution including the analyte can then be analyzed using an analytical instrument or undergo further processing.

Low density microcellular foams

DOEpatents

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

1987-01-01

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

Alcohol based-deep eutectic solvent (DES) as an alternative green additive to increase rotenone yield

NASA Astrophysics Data System (ADS)

Othman, Zetty Shafiqa; Hassan, Nur Hasyareeda; Zubairi, Saiful Irwan

2015-09-01

Deep eutectic solvents (DESs) are basically molten salts that interact by forming hydrogen bonds between two added components at a ratio where eutectic point reaches a melting point lower than that of each individual component. Their remarkable physicochemical properties (similar to ionic liquids) with remarkable green properties, low cost and easy handling make them a growing interest in many fields of research. Therefore, the objective of pursuing this study is to analyze the potential of alcohol-based DES as an extraction medium for rotenone extraction from Derris elliptica roots. DES was prepared by a combination of choline chloride, ChCl and 1, 4-butanediol at a ratio of 1/5. The structure of elucidation of DES was analyzed using FTIR, 1H-NMR and 13C-NMR. Normal soaking extraction (NSE) method was carried out for 14 hours using seven different types of solvent systems of (1) acetone; (2) methanol; (3) acetonitrile; (4) DES; (5) DES + methanol; (6) DES + acetonitrile; and (7) [BMIM] OTf + acetone. Next, the yield of rotenone, % (w/w), and its concentration (mg/ml) in dried roots were quantitatively determined by means of RP-HPLC. The results showed that a binary solvent system of [BMIM] OTf + acetone and DES + acetonitrile was the best solvent system combination as compared to other solvent systems. It contributed to the highest rotenone content of 0.84 ± 0.05% (w/w) (1.09 ± 0.06 mg/ml) and 0.84 ± 0.02% (w/w) (1.03 ± 0.01 mg/ml) after 14 hours of exhaustive extraction time. In conclusion, a combination of the DES with a selective organic solvent has been proven to have a similar potential and efficiency as of ILs in extracting bioactive constituents in the phytochemical extraction process.

Advanced model-based control strategies for the intensification of upstream and downstream processing in mAb production.

PubMed

Papathanasiou, Maria M; Quiroga-Campano, Ana L; Steinebach, Fabian; Elviro, Montaña; Mantalaris, Athanasios; Pistikopoulos, Efstratios N

2017-07-01

Current industrial trends encourage the development of sustainable, environmentally friendly processes with minimal energy and material consumption. In particular, the increasing market demand in biopharmaceutical industry and the tight regulations in product quality necessitate efficient operating procedures that guarantee products of high purity. In this direction, process intensification via continuous operation paves the way for the development of novel, eco-friendly processes, characterized by higher productivity and lower production costs. This work focuses on the development of advanced control strategies for (i) a cell culture system in a bioreactor and (ii) a semicontinuous purification process. More specifically, we consider a fed-batch culture of GS-NS0 cells and the semicontinuous Multicolumn Countercurrent Solvent Gradient Purification (MCSGP) for the purification process. The controllers are designed following the PAROC framework/software platform and their capabilities are assessed in silico, against the process models. It is demonstrated that the proposed controllers efficiently manage to increase the system productivity, returning strategies that can lead to continuous, stable process operation. © 2017 American Institute of Chemical Engineers Biotechnol. Prog., 33:966-988, 2017. © 2017 American Institute of Chemical Engineers.

Cardio-pulmonary effects of inhaled solvents: computer-assisted measurement and analysis

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

Engwall, M.J.

The physiological effects of the inhalation of three solvent vapors were measured on anesthetized dogs. The tested solvents were: acetone, ethanol, and toluene. Measurements of respiratory mechanics, pulmonary and systemic hemodynamics, cardiac output, and gas-exchange were taken while exposing the animals to the vaporized solvents. After the exposures, the animals were terminated and lung tissue and alveolar lining material (ALM) were collected. The ALM was analyzed by high performance liquid chromatography for the amounts of component phospholipids. The tissues were inspected under light microscopy for evidence of acute damage associated with the solvent exposures.

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

PubMed

Chen, Yuxia; Zhan, Chuanlang; Yao, Jiannian

2016-10-06

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

[Calculation of optic system of superfine medical endoscopes based on gradient elements].

PubMed

Díakonov, S Iu; Korolev, A V

1994-01-01

The application of gradient optic elements to rigid endoscopes decreases their diameter to 1.5-2.0 mm. The given mathematical dependences determine aperture and field characteristics, focus and focal segments, resolution of the optic systems based on gradient optics. Parameters of the gradient optic systems for superfine medical endoscopes are characterized and their practical application is shown.

GREEN CATALYZED OXIDATION OF HYDROCARBONS IN ALTERNATIVE SOLVENT SYSTEMS GENERATED BY PARIS II

EPA Science Inventory

Green Catalyzed Oxidation of Hydrocarbons in Alternative Solvent Systems Generated by PARIS II

Michael A. Gonzalez*, Thomas M. Becker, and Paul F. Harten; Sustainable Technology Division, Office of Research and Development; United States Environmental Protection Agency, 26...

Phase equilibria in fullerene-containing systems as a basis for development of manufacture and application processes for nanocarbon materials

NASA Astrophysics Data System (ADS)

Semenov, K. N.; Charykov, N. A.; Postnov, V. N.; Sharoyko, V. V.; Murin, I. V.

2016-01-01

This review is the first attempt to integrate the available data on all types of phase equilibria (solubility, extraction and sorption) in systems containing light fullerenes (C60 and C70). In the case of solubility diagrams, the following types of phase equilibria are considered: individual fullerene (C60 or C70)-solvent under polythermal and polybaric conditions; C60-C70-solvent, individual fullerene-solvent(1)-solvent(2), as well as multicomponent systems comprising a single fullerene or an industrial mixture of fullerenes and vegetable oils, animal fats or essential oils under polythermal conditions. All published experimental data on the extraction equilibria in C60-C70-liquid phase(1)-liquid phase(2) systems are described systematically and the sorption characteristics of various materials towards light fullerenes are estimated. The possibility of application of these experimental data for development of pre-chromatographic and chromatographic methods for separation of fullerene mixtures and application of fullerenes as nanomodifiers are described. The bibliography includes 87 references.

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

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

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

2012-07-25

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

Fourier Transform Infrared Spectroscopy and Multivariate Analysis for Online Monitoring of Dibutyl Phosphate Degradation Product in Tributyl Phosphate/n-Dodecane/Nitric Acid Solvent

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

Tatiana G. Levitskaia; James M. Peterson; Emily L. Campbell

2013-12-01

In liquid–liquid extraction separation processes, accumulation of organic solvent degradation products is detrimental to the process robustness, and frequent solvent analysis is warranted. Our research explores the feasibility of online monitoring of the organic solvents relevant to used nuclear fuel reprocessing. This paper describes the first phase of developing a system for monitoring the tributyl phosphate (TBP)/n-dodecane solvent commonly used to separate used nuclear fuel. In this investigation, the effect of extraction of nitric acid from aqueous solutions of variable concentrations on the quantification of TBP and its major degradation product dibutylphosphoric acid (HDBP) was assessed. Fourier transform infrared (FTIR)more » spectroscopy was used to discriminate between HDBP and TBP in the nitric acid-containing TBP/n-dodecane solvent. Multivariate analysis of the spectral data facilitated the development of regression models for HDBP and TBP quantification in real time, enabling online implementation of the monitoring system. The predictive regression models were validated using TBP/n-dodecane solvent samples subjected to high-dose external ?-irradiation. The predictive models were translated to flow conditions using a hollow fiber FTIR probe installed in a centrifugal contactor extraction apparatus, demonstrating the applicability of the FTIR technique coupled with multivariate analysis for the online monitoring of the organic solvent degradation products.« less

Fourier Transform Infrared Spectroscopy and Multivariate Analysis for Online Monitoring of Dibutyl Phosphate Degradation Product in Tributyl Phosphate /n-Dodecane/Nitric Acid Solvent

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

Levitskaia, Tatiana G.; Peterson, James M.; Campbell, Emily L.

2013-11-05

In liquid-liquid extraction separation processes, accumulation of organic solvent degradation products is detrimental to the process robustness and frequent solvent analysis is warranted. Our research explores feasibility of online monitoring of the organic solvents relevant to used nuclear fuel reprocessing. This paper describes the first phase of developing a system for monitoring the tributyl phosphate (TBP)/n-dodecane solvent commonly used to separate used nuclear fuel. In this investigation, the effect of extraction of nitric acid from aqueous solutions of variable concentrations on the quantification of TBP and its major degradation product dibutyl phosphoric acid (HDBP) was assessed. Fourier Transform Infrared Spectroscopymore » (FTIR) spectroscopy was used to discriminate between HDBP and TBP in the nitric acid-containing TBP/n-dodecane solvent. Multivariate analysis of the spectral data facilitated the development of regression models for HDBP and TBP quantification in real time, enabling online implementation of the monitoring system. The predictive regression models were validated using TBP/n-dodecane solvent samples subjected to the high dose external gamma irradiation. The predictive models were translated to flow conditions using a hollow fiber FTIR probe installed in a centrifugal contactor extraction apparatus demonstrating the applicability of the FTIR technique coupled with multivariate analysis for the online monitoring of the organic solvent degradation products.« less

Hydrophilic organic/salt-containing aqueous two-phase solvent system for counter-current chromatography: a novel technique for separation of polar compounds.

PubMed

Liu, Dan; Zou, Xiaowei; Gao, Mingzhe; Gu, Ming; Xiao, Hongbin

2014-08-22

Hydrophilic organic/salt-containing aqueous two-phase system composing of ethanol, water and ammonium sulfate for separation polar compounds was investigated on multilayer coil associated with J-type HSCCC devices. Compared to the classical polar solvent system based on 1-butanol-water or PEG1000-ammonium sulfate-water, the water content of upper phase in ethanol-ammonium sulfate-water systems was from 53.7% to 32.8% (wt%), closed to PEG1000-ammonium sulfate-water aqueous two-phase systems and higher than 1-butanol-water (22.0%, wt%). Therefore, the polarity of ethanol-ammonium sulfate-water is in the middle of 1-butanol-water and PEG-ammonium sulfate-water system, which is quite good for separating polar compounds like phenols, nucleosides and amino acids with low partition coefficient in 1-octanol-water system. The retention of stationary phase in four elution mode on type-J counter-current chromatography devices with multilayer coil column changed from 26% to 71%. Hydrodynamic trend possess both intermediate and hydrophilic solvent system property, which closely related to the composition of solvent system. The applicability of this system was demonstrated by successful separation of adenosine, uridine guanosine and cytidine. Copyright © 2014 Elsevier B.V. All rights reserved.

ACTIVE EFFLUX OF ORGANIC SOLVENTS BY PSEUDOMONAS PUTIDA S12 IS INDUCED BY SOLVENTS

EPA Science Inventory

Induction of the membrane-associated organic solvent efflux system SrpABC of Pseudomonas putida S12 was examined by cloning a 312-bp DNA fragment, containing the srp promoter, in the broad-host-range reporter vector pKRZ-1. Compounds that are capable of inducing expression of the...

Oil recovery from petroleum sludge through ultrasonic assisted solvent extraction.

PubMed

Hu, Guangji; Li, Jianbing; Huang, Shuhui; Li, Yubao

2016-09-18

The effect of ultrasonic assisted extraction (UAE) process on oil recovery from refinery oily sludge was examined in this study. Two types of UAE treatment including UAE probe (UAEP) system and UAE bath (UAEB) system were investigated. Their oil recovery efficiencies were compared to that of mechanical shaking extraction (MSE). Three solvents including cyclohexane (CHX), ethyl acetate (EA), and methyl ethyl ketone (MEK) were examined as the extraction solvents. The influence of experimental factors on oil and solvent recovery was investigated using an orthogonal experimental design. Results indicated that solvent type, solvent-to-sludge (S/S) ratio, and treatment duration could have significant effects on oil recovery in UAE treatment. Under the optimum conditions, UAEP treatment can obtain an oil recovery of 68.8% within 20 s, which was higher than that (i.e., 62.0%) by MSE treatment after 60 min' extraction. UAEB treatment can also obtain a promising oil recovery within shorter extraction duration (i.e., 15 min) than MSE. UAE was thus illustrated as an effective and improved approach for oily sludge recycling.

A mixed solvent system for preparation of spherically agglomerated crystals of ascorbic acid.

PubMed

Ren, Fuzheng; Zhou, Yaru; Liu, Yan; Fu, Jinping; Jing, Qiufang; Ren, Guobin

2017-09-01

The objective of this research was to develop a novel solvent system to prepare spherically agglomerated crystals (SAC) of ascorbic acid with improved flowability for direct compression. A spherical agglomeration method was developed by selecting the mixed solvents (n-butyl and ethyl acetate) as a poor solvent and the process was further optimized by using triangular phase diagram and particle vision measurement. Physiochemical properties of SAC were characterized and compared with original drug crystals. It showed that amount of poor solvent, ratio of solvent mixture, and drug concentration are critical for preparation of SAC with desirable properties. The solid state of SAC was same as original crystals according to DSC, XRD, and FT-IR results. There was no significant difference in solubility and dissolution rate of drug between SAC and original crystals. The flowability and packability of SAC as well as the tensile strength and elastic recovery of tablets made from SAC were all significantly improved when compared with original crystals and tablets from crystals. It is concluded that the present method was suitable to prepare SAC of ascorbic acid for direct compression.

Mesoscale Polymer Dissolution Probed by Raman Spectroscopy and Molecular Simulations

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

Chang, Tsun-Mei; Xantheas, Sotiris S.; Vasdekis, Andreas E.

2016-10-13

The diffusion of various solvents into a polystyrene (PS) matrix was probed experimentally by monitoring the temporal profiles of the Raman spectra and theoretically from molecular dynamics (MD) simulations of the binary system. The simulation results assist in providing a fundamental, molecular level connection between the mixing/dissolution processes and the difference = solvent – PS in the values of the Hildebrand parameter () between the two components of the binary systems: solvents having similar values of with PS (small ) exhibit fast diffusion into the polymer matrix, whereas the diffusion slows down considerably when the ’s are different (large ).more » To this end, the Hildebrand parameter was identified as a useful descriptor that governs the process of mixing in polymer – solvent binary systems. The experiments also provide insight into further refinements of the models specific to non-Fickian diffusion phenomena that need to be used in the simulations.« less

The synthesis and the chemical and physical properties of non-aqueous silylamine solvents for carbon dioxide capture.

PubMed

Rohan, Amy L; Switzer, Jackson R; Flack, Kyle M; Hart, Ryan J; Sivaswamy, Swetha; Biddinger, Elizabeth J; Talreja, Manish; Verma, Manjusha; Faltermeier, Sean; Nielsen, Paul T; Pollet, Pamela; Schuette, George F; Eckert, Charles A; Liotta, Charles L

2012-11-01

Silylamine reversible ionic liquids were designed to achieve specific physical properties in order to address effective CO₂ capture. The reversible ionic liquid systems reported herein represent a class of switchable solvents where a relatively non-polar silylamine (molecular liquid) is reversibly transformed to a reversible ionic liquid (RevIL) by reaction with CO₂ (chemisorption). The RevILs can further capture additional CO₂ through physical absorption (physisorption). The effects of changes in structure on (1) the CO₂ capture capacity (chemisorption and physisorption), (2) the viscosity of the solvent systems at partial and total conversion to the ionic liquid state, (3) the energy required for reversing the CO₂ capture process, and (4) the ability to recycle the solvents systems are reported. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Reactive extraction at liquid-liquid systems

NASA Astrophysics Data System (ADS)

Wieszczycka, Karolina

2018-01-01

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

Application of mass spectrometer-inverse gas chromatography to study polymer-solvent diffusivity and solubility.

PubMed

Galdámez, J Román; Danner, Ronald P; Duda, J Larry

2007-07-20

The application of a mass spectrometer detector in capillary column inverse gas chromatography is shown to be a valuable tool in the measurement of diffusion and solubility in polymer-solvent systems. The component specific detector provides excellent results for binary polymer-solvent systems, but it is particularly valuable because it can be readily applied to multicomponent systems. Results for a number of infinitely dilute solvents in poly(vinyl acetate) (PVAc) are reported over a range of temperature from 60 to 150 degrees C. Results are also reported for finite concentrations of toluene and methanol in PVAc from 60 to 110 degrees C. Finally, the technique was applied to study the effect of finite concentrations of toluene on the diffusion coefficients of THF and cyclohexane in PVAc. The experimental data compare well with literature values for both infinite and finite concentrations, indicating that the experimental protocol described in this work is sound.

Ion conducting polymers and polymer blends for alkali metal ion batteries

DOEpatents

DeSimone, Joseph M.; Pandya, Ashish; Wong, Dominica; Vitale, Alessandra

2017-08-29

Electrolyte compositions for batteries such as lithium ion and lithium air batteries are described. In some embodiments the compositions are liquid compositions comprising (a) a homogeneous solvent system, said solvent system comprising a perfluropolyether (PFPE) and polyethylene oxide (PEO); and (b) an alkali metal salt dissolved in said solvent system. In other embodiments the compositions are solid electrolyte compositions comprising: (a) a solid polymer, said polymer comprising a crosslinked product of a crosslinkable perfluropolyether (PFPE) and a crosslinkable polyethylene oxide (PEO); and (b) an alkali metal ion salt dissolved in said polymer. Batteries containing such compositions as electrolytes are also described.

Molecular and ionic diffusion in aqueous - deep eutectic solvent mixtures: probing inter-molecular interactions using PFG NMR.

PubMed

D'Agostino, Carmine; Gladden, Lynn F; Mantle, Mick D; Abbott, Andrew P; Ahmed, Essa I; Al-Murshedi, Azhar Y M; Harris, Robert C

2015-06-21

Pulsed field gradient (PFG) NMR has been used to probe self-diffusion of molecular and ionic species in aqueous mixtures of choline chloride (ChCl) based deep eutectic solvents (DESs), in order to elucidate the effect of water on motion and inter-molecular interactions between the different species in the mixtures, namely the Ch(+) cation and hydrogen bond donor (HBD). The results reveal an interesting and complex behaviour of such mixtures at a molecular level. In general, it is observed that the hydroxyl protons ((1)H) of Ch(+) and the hydrogen bond donor have diffusion coefficients significantly different from those measured for their parent molecules when water is added. This indicates a clear and significant change in inter-molecular interactions. In aqueous Ethaline, the hydroxyl species of Ch(+) and HBD show a stronger interaction with water as water is added to the system. In the case of Glyceline, water has little effect on both hydroxyl proton diffusion of Ch(+) and HBD. In Reline, it is likely that water allows the formation of small amounts of ammonium hydroxide. The most surprising observation is from the self-diffusion of water, which is considerably higher that expected from a homogeneous liquid. This leads to the conclusion that Reline and Glyceline form mixtures that are inhomogeneous at a microscopic level despite the hydrophilicity of the salt and HBD. This work shows that PFG NMR is a powerful tool to elucidate both molecular dynamics and inter-molecular interactions in complex liquid mixtures, such as the aqueous DES mixtures.

On-line coupling of counter-current chromatography and macroporous resin chromatography for continuous isolation of arctiin from the fruit of Arctium lappa L.

PubMed

Guo, Mengzhe; Liang, Junling; Wu, Shihua

2010-08-13

In this work, we have developed a novel hybrid two-dimensional counter-current chromatography and liquid chromatography (2D CCC x LC) system for the continuous purification of arctiin from crude extract of Arctium lappa. The first dimensional CCC column has been designed to fractionalize crude complex extract into pure arctiin effluent using a one-component organic/salt-containing system, and the second dimensional LC column has been packed with macroporous resin for on-line adsorption, desalination and desorption of arctiin which was effluent purified from the first CCC dimension. Thus, the crude arctiin mixture has been purified efficiently and conveniently by on-line CCC x LC in spite of the use of a salt-containing solvent system in CCC separation. As a result, high purity (more than 97%) of arctiin has been isolated by repeated injections both using the ethyl acetate-8% sodium chloride aqueous solution and butanol-1% sodium chloride aqueous solution. By contrast with the traditional CCC processes using multi-component organic/aqueous solvent systems, the present on-line CCC x LC process only used a one-component organic solvent and thus the solvent is easier to recover and regenerate. All of used solvents such as ethyl acetate, n-butanol and NaCl aqueous solution are low toxicity and environment-friendly. Moreover, the lower phase of salt-containing aqueous solution used as mobile phase, only contained minor organic solvent, which will save much organic solvent in continuous separation. In summary, our results indicated that the on-line hybrid 2D CCC x LC system using one-component organic/salt-containing aqueous solution is very promising and powerful tool for high-throughput purification of arctiin from fruits of A. lappa. 2010 Elsevier B.V. All rights reserved.

Gradient pre-emphasis to counteract first-order concomitant fields on asymmetric MRI gradient systems.

PubMed

Tao, Shengzhen; Weavers, Paul T; Trzasko, Joshua D; Shu, Yunhong; Huston, John; Lee, Seung-Kyun; Frigo, Louis M; Bernstein, Matt A

2017-06-01

To develop a gradient pre-emphasis scheme that prospectively counteracts the effects of the first-order concomitant fields for any arbitrary gradient waveform played on asymmetric gradient systems, and to demonstrate the effectiveness of this approach using a real-time implementation on a compact gradient system. After reviewing the first-order concomitant fields that are present on asymmetric gradients, we developed a generalized gradient pre-emphasis model assuming arbitrary gradient waveforms to counteract their effects. A numerically straightforward, easily implemented approximate solution to this pre-emphasis problem was derived that was compatible with the current hardware infrastructure of conventional MRI scanners for eddy current compensation. The proposed method was implemented on the gradient driver subsystem, and its real-time use was tested using a series of phantom and in vivo data acquired from two-dimensional Cartesian phase-difference, echo-planar imaging, and spiral acquisitions. The phantom and in vivo results demonstrated that unless accounted for, first-order concomitant fields introduce considerable phase estimation error into the measured data and result in images with spatially dependent blurring/distortion. The resulting artifacts were effectively prevented using the proposed gradient pre-emphasis. We have developed an efficient and effective gradient pre-emphasis framework to counteract the effects of first-order concomitant fields of asymmetric gradient systems. Magn Reson Med 77:2250-2262, 2017. © 2016 International Society for Magnetic Resonance in Medicine. © 2016 International Society for Magnetic Resonance in Medicine.

REMOVAL OF PCBS FROM A CONTAMINATED SOIL USING CF-SYSTEMS SOLVENT EXTRACTION PROCESS

EPA Science Inventory

The US EPA's START team in cooperation with EPA's SITE program evaluated a pilot scale solvent extraction process developed by CF-Systems. This process uses liquified propane to extract organic contaminants from soils, sludges, and sediments. A pilot-scale evaluation was conducte...

40 CFR 63.4351 - How do I demonstrate initial compliance?

Code of Federal Regulations, 2013 CFR

2013-07-01

... the organic HAP emissions reductions by applying the volatile organic matter collection and recovery... cumulative amount of volatile organic matter recovered by the solvent recovery system for the compliance... of the mass of volatile organic matter recovered. (ii) For each solvent recovery system, determine...

40 CFR 63.4351 - How do I demonstrate initial compliance?

Code of Federal Regulations, 2014 CFR

2014-07-01

... the organic HAP emissions reductions by applying the volatile organic matter collection and recovery... cumulative amount of volatile organic matter recovered by the solvent recovery system for the compliance... of the mass of volatile organic matter recovered. (ii) For each solvent recovery system, determine...

40 CFR 63.4351 - How do I demonstrate initial compliance?

Code of Federal Regulations, 2012 CFR

2012-07-01

... the organic HAP emissions reductions by applying the volatile organic matter collection and recovery... cumulative amount of volatile organic matter recovered by the solvent recovery system for the compliance... of the mass of volatile organic matter recovered. (ii) For each solvent recovery system, determine...

Integration of living cells into nanostructures using non-conventional self-assembly

NASA Astrophysics Data System (ADS)

Carnes, Eric C.

Patternable cell immobilization is an essential feature of any solid-state device designed for interrogating or exploiting living cells. Immobilized cells must remain viable in a robust matrix that promotes fluidic connectivity between the cells and their environment while retaining the ability to establish and maintain necessary chemical gradients. A suitable inorganic matrix can be constructed via evaporation-induced self-assembly of nanostructured silica, in which phospholipids are used in place of traditional surfactant structure-directing agents in order to enhance cell viability and to create a coherent interface between the cell and the surrounding three-dimensional nanostructure. We have used this technique to develop two distinct cell encapsulation processes: cell-directed assembly and cell-directed integration. Cell-directed assembly is a one-step procedure that provides superior viability of immobilized cells by encouraging cells to interact with the developing host matrix. Limitations of this system include low viability for some cell types due to exposure to solvents and stresses, as well as a lack of control over the developing host nanostructure. Cell-directed integration addresses these shortcomings by introducing a two-step process in which cells become encapsulated in a pre-formed silica matrix. The validity of each encapsulation method has been demonstrated with Gram-positive and Gram-negative bacteria, yeast, and mammalian cells. The ability of the immobilized cells to establish relevant gradients of ions or signaling molecules, a key feature of these systems, has been characterized. Additionally, extension of cell encapsulation to address lingering questions in cell biology is addressed. We have also adapted these immobilization processes to be compatible with a variety of patterning strategies having tailorable properties. Widely available photolithography techniques, as well as direct aerosol deposition, have been adapted to provide methods for obtaining both positive and negative transfer of desired cell patterns. Multi-step lithography is also used to create a highly functional system allowing spatial control of not only cells but also media and other molecules of interest.

Spray drying from organic solvents to prepare nanoporous/nanoparticulate microparticles of protein: excipient composites designed for oral inhalation.

PubMed

Ní Ógáin, Orla; Tajber, Lidia; Corrigan, Owen I; Healy, Anne Marie

2012-09-01

The aim of this study was to determine if spray-drying could successfully produce microparticles containing the model protein trypsin in a form suitable for inhalation. Trypsin was spray-dried with raffinose from a methanol : n-butyl acetate solvent system (MeOH : BA). The solvent system was then adjusted to include water, and trypsin was co-spray-dried with raffinose, trehalose or hydroxpropyl-β-cyclodextrin. The spray-dried products were characterised by SEM, XRD, DSC, TGA and FTIR. Protein biological activity and in-vitro deposition of trypsin : excipient nanoporous/nanoparticulate microparticles (NPMPs) was also assessed. The inclusion of water in a MeOH : BA solvent system allowed for the successful production of NPMPs of trypsin : excipient by spray-drying. Trypsin formulated as trypsin : excipient NPMPs retained biological activity on processing and showed no deterioration in activity or morphological characteristics when stored with desiccant at either 4 or 25°C. Hydroxpropyl-β-cyclodextrin showed advantages over the sugars in terms of producing powders with appropriate density and with greater physical stability under high-humidity conditions. Fine particle fractions of between 41 and 45% were determined for trypsin : excipient NPMPs. NPMPs of trypsin : excipient systems can be produced by spray-drying by adjustment of the solvent system to allow for adequate solubility of trypsin. © 2012 The Authors. JPP © 2012 Royal Pharmaceutical Society.

Hand-Portable Gradient Capillary Liquid Chromatography Pumping System.

PubMed

Sharma, Sonika; Plistil, Alex; Barnett, Hal E; Tolley, H Dennis; Farnsworth, Paul B; Stearns, Stanley D; Lee, Milton L

2015-10-20

In this work, a novel splitless nanoflow gradient generator integrated with a stop-flow injector was developed and evaluated using an on-column UV-absorption detector. The gradient pumping system consisted of two nanoflow pumps controlled by micro stepper motors, a mixer connected to a serpentine tube, and a high-pressure valve. The gradient system weighed only 4 kg (9 lbs) and could generate up to 55 MPa (8000 psi) pressure. The system could operate using a 24 V DC battery and required 1.2 A for operation. The total volume capacity of the pump was 74 μL, and a sample volume of 60 nL could be injected. The system provided accurate nanoflow rates as low as 10 nL/min without employing a splitter, making it ideal for capillary column use. The gradient dwell volume was calculated to be 1.3 μL, which created a delay of approximately 4 min with a typical flow rate of 350 nL/min. Gradient performance was evaluated for gradient step accuracy, and excellent reproducibility was obtained in day-to-day experiments (RSD < 1.2%, n = 4). Linear gradient reproducibility was tested by separating a three-component pesticide mixture on a poly(ethylene glycol) diacrylate (PEGDA) monolithic column. The retention time reproducibility was very good in run-to-run experiments (RSD < 1.42%, n = 4). Finally, excellent separation of five phenols was demonstrated using the nanoflow gradient system.

Self-thermophoresis and thermal self-diffusion in liquids and gases.

PubMed

Brenner, Howard

2010-09-01

This paper demonstrates the existence of self-thermophoresis, a phenomenon whereby a virtual thermophoretic force arising from a temperature gradient in a quiescent single-component liquid or gas acts upon an individual molecule of that fluid in much the same manner as a "real" thermophoretic force acts upon a macroscopic, non-Brownian body immersed in that same fluid. In turn, self-thermophoresis acting in concert with Brownian self-diffusion gives rise to the phenomenon of thermal self-diffusion in single-component fluids. The latter furnishes quantitative explanations of both thermophoresis in pure fluids and thermal diffusion in binary mixtures (the latter composed of a dilute solution of a physicochemically inert solute whose molecules are large compared with those of the solvent continuum). Explicitly, the self-thermophoretic theory furnishes a simple expression for both the thermophoretic velocity U of a macroscopic body in a single-component fluid subjected to a temperature gradient ∇T , and the intimately related binary thermal diffusion coefficient D{T} for a two-component colloidal or macromolecular mixture. The predicted expressions U=-D{T}∇T≡-βD{S}∇T and D{T}=βD{S} (with β and D{S} the pure solvent's respective thermal expansion and isothermal self-diffusion coefficients) are each noted to accord reasonably well with experimental data for both liquids and gases. The likely source of systematic deviations of the predicted values of D{T} from these data is discussed. This appears to be the first successful thermodiffusion theory applicable to both liquids and gases, a not insignificant achievement considering that the respective thermal diffusivities and thermophoretic velocities of these two classes of fluids differ by as much as six orders of magnitude.

Sweeping as a multistep enrichment process in micellar electrokinetic chromatography: the retention factor gradient effect.

PubMed

El-Awady, Mohamed; Pyell, Ute

2013-07-05

The application of a new method developed for the assessment of sweeping efficiency in MEKC under homogeneous and inhomogeneous electric field conditions is extended to the general case, in which the distribution coefficient and the electric conductivity of the analyte in the sample zone and in the separation compartment are varied. As test analytes p-hydroxybenzoates (parabens), benzamide and some aromatic amines are studied under MEKC conditions with SDS as anionic surfactant. We show that in the general case - in contrast to the classical description - the obtainable enrichment factor is not only dependent on the retention factor of the analyte in the sample zone but also dependent on the retention factor in the background electrolyte (BGE). It is shown that in the general case sweeping is inherently a multistep focusing process. We describe an additional focusing/defocusing step (the retention factor gradient effect, RFGE) quantitatively by extending the classical equation employed for the description of the sweeping process with an additional focusing/defocusing factor. The validity of this equation is demonstrated experimentally (and theoretically) under variation of the organic solvent content (in the sample and/or the BGE), the type of organic solvent (in the sample and/or the BGE), the electric conductivity (in the sample), the pH (in the sample), and the concentration of surfactant (in the BGE). It is shown that very high enrichment factors can be obtained, if the pH in the sample zone makes possible to convert the analyte into a charged species that has a high distribution coefficient with respect to an oppositely charged micellar phase, while the pH in the BGE enables separation of the neutral species under moderate retention factor conditions. Copyright © 2013 Elsevier B.V. All rights reserved.

Effects of solvent drying time on micro-shear bond strength and mechanical properties of two self-etching adhesive systems.

PubMed

Sadr, Alireza; Shimada, Yasushi; Tagami, Junji

2007-09-01

The all-in-one adhesives are simplified forms of two-step self-etching adhesive systems that must be air dried to remove solvent and water before curing. It was investigated whether those two systems perform equally well and if their performance is affected by air-drying of the solvent containing agent. Two adhesive systems (both by Kuraray Medical) were evaluated; Clearfil Tri-S bond (TS) and Clearfil SE bond (SE). Micro-shear bond strengths to human dentin after solvent air-drying times of 2, 5 or 10 s for each group were measured (n=10). The indentation creep and hardness of the bonding layer were also determined for each group. The lowest micro-shear bond strength, nano-indentation hardness and creep stress exponents were obtained for 2 s air dried specimens of each material. After 10 s air blowing, SE showed superior properties compared to TS groups (p<0.05). When properly handled, two step self-etching material performs better than the all-in-one adhesive. Air-drying is a crucial step in the application of solvent containing adhesives and may affect the overall clinical performance of them, through changes in the bond strength and altering nano-scale mechanical properties.

Enhanced Furfural Yields from Xylose Dehydration in the gamma-Valerolactone/Water Solvent System at Elevated Temperatures.

PubMed

Sener, Canan; Motagamwala, Ali Hussain; Alonso, David Martin; Dumesic, James

2018-05-18

High yields of furfural (>90%) were achieved from xylose dehydration in a sustainable solvent system composed of -valerolactone (GVL), a biomass derived solvent, and water. It is identified that high reaction temperatures (e.g., 498 K) are required to achieve high furfural yield. Additionally, it is shown that the furfural yield at these temperatures is independent of the initial xylose concentration, and high furfural yield is obtained for industrially relevant xylose concentrations (10 wt%). A reaction kinetics model is developed to describe the experimental data obtained with solvent system composed of 80 wt% GVL and 20 wt% water across the range of reaction conditions studied (473 - 523 K, 1-10 mM acid catalyst, 66 - 660 mM xylose concentration). The kinetic model demonstrates that furfural loss due to bimolecular condensation of xylose and furfural is minimized at elevated temperature, whereas carbon loss due to xylose degradation increases with increasing temperature. Accordingly, the optimal temperature range for xylose dehydration to furfural in the GVL/H2O solvent system is identified to be from 480 to 500 K. Under these reaction conditions, furfural yield of 93% is achieved at 97% xylan conversion from lignocellulosic biomass (maple wood). © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Two-column sequential injection chromatography--new approach for fast and effective analysis and its comparison with gradient elution chromatography.

PubMed

Chocholous, Petr; Satínský, Dalibor; Sklenárová, Hana; Solich, Petr

2010-05-23

This work presents novel approach in low-pressure chromatography flow systems--two-column Sequential Injection Chromatography (2-C SIC) and its comparison with gradient elution chromatography on the same instrument. The system was equipped with two different chromatographic columns (connected to selection valve in parallel design) for isocratic separation and determination of all components in composed anti-inflammatory pharmaceutical preparation (tablets). The sample was first injected on the first column of length 30 mm where less retained analytes were separated and then the sample was injected on the second column of length 10 mm where more retained analytes were separated. The SIC system was based on a commercial SIChrom manifold (8-port high-pressure selection valve and medium-pressure syringe pump with 4 mL reservoir) (FIAlab, USA) with two commercially available monolithic columns the "first column" Chromolith Flash RP-18e (25 mm x 4.6 mm i.d. with guard column 5 mm x 4.6 mm i.d.) and the "second column" Chromolith RP-18e (10 mm x 4.6 mm i.d.) and CCD UV-vis detector USB 4000 with micro-volume 1.0 cm Z flow cell. Two mobile phases were used for analysis (one for each column). The mobile phase 1 used for elution of paracetamol, caffeine and salicylic acid (internal standard) was acetonitrile/water (10:90, v/v, the water part of pH 3.5 adjusted with acetic acid), flow rate was 0.9 mL min(-1) (volume 3.0 mL of mobile phase per analysis). The mobile phase 2 used for elution of propyphenazone was acetonitrile/water (30:70, v/v); flow rate was 1.2 mL min(-1) (volume 1.5 mL of mobile phase per analysis). Absorbance was monitored at 210 nm. Samples were prepared by dissolving of one tablet in 30% acetonitrile and 10 microL of filtered supernatant was injected on each column (2 x 10 microL). The chromatographic resolution between all compounds was >1.45 and analysis time was 5.5 min under the optimal conditions. Limits of detection were determined at 0.4 microg mL(-1) for paracetamol, at 0.5 microg mL(-1) for caffeine and at 0.7 microg mL(-1) for propyphenazone. The new two-column chromatographic set-up developed as an alternative approach to gradient elution chromatography shows evident advantages (time and solvent reduction more than one-third) as compared with single-column gradient SIC method with Chromolith Flash RP-18 (25 mm x 4.6 mm i.d. with guard column 5 mm x 4.6 mm i.d.). Copyright 2010 Elsevier B.V. All rights reserved.

Handbook for Repairing Nonconventional Roofing Systems

DTIC Science & Technology

1988-12-01

membrane. 61 PIMB (solvent) Figure 71. Apply welding solvent to the PIB patch. Figure 72. Work the solvent Into the P113 patch. Pila 62 (solvent) Figure 73...when exposed to flame but will not burn nor support combustion . PVC repair techniques are basically the same as for a new application of a PVC fully...granules (if desired) before the final coat dries. 83 PUF F4gue 102. Remove the damaged material and bevel the s! des of the hole. 4󈧵, Figure 103. Trim th

Cosolvent effects on the drug release and depot swelling in injectable in situ depot-forming systems.

PubMed

Liu, Hui; Venkatraman, Subbu S

2012-05-01

Although injectable depot-forming solutions have been commercialized, the factors that influence the overall release kinetics from such systems are still not fully understood. In this work, we address the effect of cosolvent on the issue of excessive burst release of potent bioactives from injectable depot-forming solutions. Specifically, we have evaluated the influence of addition of a relatively hydrophobic cosolvent (triacetin) to more hydrophilic biocompatible solvents such as dimethyl sulfoxide (DMSO) and N-methyl-2-pyrrolidone (NMP) on the burst release. Drug release and solvent release results demonstrate that high burst release that occurred when only hydrophilic solvent was used as solvent was significantly reduced by adding triacetin as a cosolvent. The profiles of drug release were in good agreement with the profiles of the hydrophilic solvent DMSO or NMP release, and the suppression of the burst by triacetin addition is due to the suppression of the solvent release. Surprisingly, the swelling of the depot increased with triacetin amount and the depot morphology became more porous compared with the absence of triacetin. Usage of hydrophobic solvent as a cosolvent to reduce the burst release was shown to be more effective on the hydrophobic PdlLA depot and less effective on the relatively hydrophilic RG502 depot. Copyright © 2012 Wiley Periodicals, Inc.

Tuning Structural Properties of Biocompatible Block Copolymer Micelles by Varying Solvent Composition

NASA Astrophysics Data System (ADS)

Cooksey, Tyler; Singh, Avantika; Mai Le, Kim; Wang, Shu; Kelley, Elizabeth; He, Lilin; Vajjala Kesava, Sameer; Gomez, Enrique; Kidd, Bryce; Madsen, Louis; Robertson, Megan

The self-assembly of block copolymers into micelles when introduced to selective solvents enables a wide array of applications, ranging from drug delivery to personal care products to nanoreactors. In order to probe the assembly and dynamics of micellar systems, the structural properties and solvent uptake of biocompatible poly(ethylene oxide-b- ɛ-caprolactone) (PEO-PCL) diblock copolymers in deuterated water (D2O) / tetrahydrofuran (THFd8) mixtures were investigated using small-angle neutron scattering in combination with nuclear magnetic resonance. PEO-PCL block copolymers, of varying molecular weight yet constant block ratio, formed spherical micelles through a wide range of solvent compositions. Varying the composition from 10 to 60 % by volume THFd8\\ in D2O / THFd8 mixtures was a means of varying the core-corona interfacial tension in the micelle system. An increase in THFd8 content in the bulk solvent increased the solvent uptake within the micelle core, which was comparable for the two series, irrespective of the polymer molecular weight. Differences in the behaviors of the micelle size parameters as the solvent composition varied originated from the differing trends in aggregation number for the two micelle series. Incorporation of the known unimer content determined from NMR allowed refinement of extracted micelle parameters.

Systems and methods for producing metal clusters; functionalized surfaces; and droplets including solvated metal ions

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

Cooks, Robert Graham; Li, Anyin; Luo, Qingjie

The invention generally relates to systems and methods for producing metal clusters; functionalized surfaces; and droplets including solvated metal ions. In certain aspects, the invention provides methods that involve providing a metal and a solvent. The methods additionally involve applying voltage to the solvated metal to thereby produce solvent droplets including ions of the metal containing compound, and directing the solvent droplets including the metal ions to a target. In certain embodiments, once at the target, the metal ions can react directly or catalyze reactions.

Biocatalytic transformations in ionic liquids.

PubMed

van Rantwijk, Fred; Madeira Lau, Rute; Sheldon, Roger A

2003-03-01

Room temperature ionic liquids are non-volatile, thermally stable and highly polar; they are also moderately hydrophilic solvents. Here, we discuss their use as reaction media for biocatalysis. Enzymes of widely diverging types are catalytically active in ionic liquids or aqueous biphasic ionic liquid systems. Lipases, in particular, maintain their activity in anhydrous ionic liquid media; the (enantio)selectivity and operational stability are often better than in traditional media. The unconventional solvent properties of ionic liquids have been exploited in biocatalyst recycling and product recovery schemes that are not feasible with traditional solvent systems.

System and process for capture of H.sub.2S from gaseous process streams and process for regeneration of the capture agent

DOEpatents

Heldenbrant, David J; Koech, Phillip K; Rainbolt, James E; Bearden, Mark D; Zheng, Feng

2014-02-18

A system and process are disclosed for selective removal and recovery of H.sub.2S from a gaseous volume, e.g., from natural gas. Anhydrous organic, sorbents chemically capture H.sub.2S gas to form hydrosulfide salts. Regeneration of the capture solvent involves addition of an anti-solvent that releases the captured H.sub.2S gas from the capture sorbent. The capture sorbent and anti-solvent are reactivated for reuse, e.g., by simple distillation.

Systems and methods for producing metal clusters; functionalized surfaces; and droplets including solvated metal ions

DOEpatents

Cooks, Robert Graham; Li, Anyin; Luo, Qingjie

2017-01-24

The invention generally relates to systems and methods for producing metal clusters; functionalized surfaces; and droplets including solvated metal ions. In certain aspects, the invention provides methods that involve providing a metal and a solvent. The methods additionally involve applying voltage to the solvated metal to thereby produce solvent droplets including ions of the metal containing compound, and directing the solvent droplets including the metal ions to a target. In certain embodiments, once at the target, the metal ions can react directly or catalyze reactions.

Fragrance compounds and amphiphilic association structures.

PubMed

Friberg, S E

1998-05-01

Fragrance formulations have traditionally been based on alcohol as the solvent, but the recent legal restrictions on volatile organic solvents have prompted the industry to change to aqueous solubilized systems. The article reviews the fundamental factors in the application of such systems evaluating the influence by different amphiphilic association structures on the vapor pressure of fragrance compounds. This information is subsequently used to estimate the variation of fragrance compound vapor pressures during evaporation. The results reveal that the vapor pressure versus time variation is improved compared to solvent-based formulations.

Rectification of nanopores in aprotic solvents - transport properties of nanopores with surface dipoles

NASA Astrophysics Data System (ADS)

Plett, Timothy; Shi, Wenqing; Zeng, Yuhan; Mann, William; Vlassiouk, Ivan; Baker, Lane A.; Siwy, Zuzanna S.

2015-11-01

Nanopores have become a model system to understand transport properties at the nanoscale. We report experiments and modeling of ionic current in aprotic solvents with different dipole moments through conically shaped nanopores in a polycarbonate film and through glass nanopipettes. We focus on solutions of the salt LiClO4, which is of great importance in modeling lithium based batteries. Results presented suggest ion current rectification observed results from two effects: (i) adsorption of Li+ ions to the pore walls, and (ii) a finite dipole moment rendered by adsorbed solvent molecules. Properties of surfaces in various solvents were probed by means of scanning ion conductance microscopy, which confirmed existence of an effectively positive surface potential in aprotic solvents with high dipole moments.Nanopores have become a model system to understand transport properties at the nanoscale. We report experiments and modeling of ionic current in aprotic solvents with different dipole moments through conically shaped nanopores in a polycarbonate film and through glass nanopipettes. We focus on solutions of the salt LiClO4, which is of great importance in modeling lithium based batteries. Results presented suggest ion current rectification observed results from two effects: (i) adsorption of Li+ ions to the pore walls, and (ii) a finite dipole moment rendered by adsorbed solvent molecules. Properties of surfaces in various solvents were probed by means of scanning ion conductance microscopy, which confirmed existence of an effectively positive surface potential in aprotic solvents with high dipole moments. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr06340j

Strong solutions and instability for the fitness gradient system in evolutionary games between two populations

NASA Astrophysics Data System (ADS)

Xu, Qiuju; Belmonte, Andrew; deForest, Russ; Liu, Chun; Tan, Zhong

2017-04-01

In this paper, we study a fitness gradient system for two populations interacting via a symmetric game. The population dynamics are governed by a conservation law, with a spatial migration flux determined by the fitness. By applying the Galerkin method, we establish the existence, regularity and uniqueness of global solutions to an approximate system, which retains most of the interesting mathematical properties of the original fitness gradient system. Furthermore, we show that a Turing instability occurs for equilibrium states of the fitness gradient system, and its approximations.

SAGE FOR MACINTOSH (MSAGE) VERSION 1.0 SOLVENT ALTERNATIVES GUIDE - USER'S GUIDE

EPA Science Inventory

The guide provides instructions for using the Solvent Alternatives Guide (SAGE) for Macintosh, version 1.0. The guide assumes that the user is familiar with the fundamentals of operating a
Macintosh personal computer under the System 7.0 (or higher) operating system. SAGE for ...

40 CFR 63.3541 - How do I demonstrate initial compliance?

Code of Federal Regulations, 2011 CFR

2011-07-01

... matter collection and recovery efficiency to the mass of organic HAP contained in the coatings and... cumulative amount of volatile organic matter recovered by the solvent recovery system each month. (2) For each solvent recovery system, determine the mass of volatile organic matter recovered for the month, kg...

40 CFR 63.3541 - How do I demonstrate initial compliance?

Code of Federal Regulations, 2013 CFR

2013-07-01

... volatile organic matter collection and recovery efficiency to the mass of organic HAP contained in the... indicates the cumulative amount of volatile organic matter recovered by the solvent recovery system each month. (2) For each solvent recovery system, determine the mass of volatile organic matter recovered for...

40 CFR 63.3541 - How do I demonstrate initial compliance?

Code of Federal Regulations, 2014 CFR

2014-07-01

... volatile organic matter collection and recovery efficiency to the mass of organic HAP contained in the... indicates the cumulative amount of volatile organic matter recovered by the solvent recovery system each month. (2) For each solvent recovery system, determine the mass of volatile organic matter recovered for...

40 CFR 63.4561 - How do I demonstrate initial compliance?

Code of Federal Regulations, 2012 CFR

2012-07-01

... reduction by applying the volatile organic matter collection and recovery efficiency to the mass of organic... cumulative amount of volatile organic matter recovered by the solvent recovery system each month. The device... volatile organic matter recovered. (2) For each solvent recovery system, determine the mass of volatile...

40 CFR 63.3541 - How do I demonstrate initial compliance?

Code of Federal Regulations, 2010 CFR

2010-07-01

... matter collection and recovery efficiency to the mass of organic HAP contained in the coatings and... cumulative amount of volatile organic matter recovered by the solvent recovery system each month. (2) For each solvent recovery system, determine the mass of volatile organic matter recovered for the month, kg...

40 CFR 63.3541 - How do I demonstrate initial compliance?

Code of Federal Regulations, 2012 CFR

2012-07-01

... volatile organic matter collection and recovery efficiency to the mass of organic HAP contained in the... indicates the cumulative amount of volatile organic matter recovered by the solvent recovery system each month. (2) For each solvent recovery system, determine the mass of volatile organic matter recovered for...

Fast analysis of capsaicinoids in Naga Jolokia extracts (Capsicum chinense) by high-performance liquid chromatography using fused core columns.

PubMed

Stipcovich, Tea; Barbero, Gerardo F; Ferreiro-González, Marta; Palma, Miguel; Barroso, Carmelo G

2018-01-15

A rapid high-performance liquid chromatography method with a C18 reverse-phase fused-core column has been developed for the determination and quantification of the main capsaicinoids (nornordihydrocapsaicin, nordihydrocapsaicin, capsaicin, dihydrocapsaicin, homocapsaicin and homodihydrocapsaicin) present in Naga Jolokia peppers. A fused-core Kinetex™ C18 column (50×2.1mm i.d.; 2.6μm) was used for the analysis. The chromatographic separation was obtained with a gradient method in which the mobile phase was water (0.1% acetic acid) as solvent A and acetonitrile (0.1% acetic acid) as solvent B. The separation of all compounds was achieved in less than 3min with a total analysis time (sample-to-sample) of 10min. The robustness of the method was evaluated. The method showed excellent repeatability and intermediate precision expressed as coefficient of variance of less than 2%. The developed method was employed for the quantification of the major capsaicinoids present in different peppers and commercial products containing chilli peppers. Copyright © 2017 Elsevier Ltd. All rights reserved.

Moving zone Marangoni drying of wet objects using naturally evaporated solvent vapor

DOEpatents

Britten, Jerald A.

1997-01-01

A surface tension gradient driven flow (a Marangoni flow) is used to remove the thin film of water remaining on the surface of an object following rinsing. The process passively introduces by natural evaporation and diffusion of minute amounts of alcohol (or other suitable material) vapor in the immediate vicinity of a continuously refreshed meniscus of deionized water or another aqueous-based, nonsurfactant rinsing agent. Used in conjunction with cleaning, developing or wet etching application, rinsing coupled with Marangoni drying provides a single-step process for 1) cleaning, developing or etching, 2) rinsing, and 3) drying objects such as flat substrates or coatings on flat substrates without necessarily using heat, forced air flow, contact wiping, centrifugation or large amounts of flammable solvents. This process is useful in one-step cleaning and drying of large flat optical substrates, one-step developing/rinsing and drying or etching/rinsing/drying of large flat patterned substrates and flat panel displays during lithographic processing, and room-temperature rinsing/drying of other large parts, sheets or continuous rolls of material.

Moving zone Marangoni drying of wet objects using naturally evaporated solvent vapor

DOEpatents

Britten, J.A.

1997-08-26

A surface tension gradient driven flow (a Marangoni flow) is used to remove the thin film of water remaining on the surface of an object following rinsing. The process passively introduces by natural evaporation and diffusion of minute amounts of alcohol (or other suitable material) vapor in the immediate vicinity of a continuously refreshed meniscus of deionized water or another aqueous-based, nonsurfactant rinsing agent. Used in conjunction with cleaning, developing or wet etching application, rinsing coupled with Marangoni drying provides a single-step process for (1) cleaning, developing or etching, (2) rinsing, and (3) drying objects such as flat substrates or coatings on flat substrates without necessarily using heat, forced air flow, contact wiping, centrifugation or large amounts of flammable solvents. This process is useful in one-step cleaning and drying of large flat optical substrates, one-step developing/rinsing and drying or etching/rinsing/drying of large flat patterned substrates and flat panel displays during lithographic processing, and room-temperature rinsing/drying of other large parts, sheets or continuous rolls of material. 5 figs.

Finely controlled multimetallic nanocluster catalysts for solvent-free aerobic oxidation of hydrocarbons

PubMed Central

Takahashi, Masaki; Koizumi, Hiromu; Chun, Wang-Jae; Kori, Makoto; Imaoka, Takane; Yamamoto, Kimihisa

2017-01-01

The catalytic activity of alloy nanoparticles depends on the particle size and composition ratio of different metals. Alloy nanoparticles composed of Pd, Pt, and Au are widely used as catalysts for oxidation reactions. The catalytic activities of Pt and Au nanoparticles in oxidation reactions are known to increase as the particle size decreases and to increase on the metal-metal interface of alloy nanoparticles. Therefore, multimetallic nanoclusters (MNCs) around 1 nm in diameter have potential as catalysts for oxidation reactions. However, there have been few reports describing the preparation of uniform alloy nanoclusters. We report the synthesis of finely controlled MNCs (around 1 nm) using a macromolecular template with coordination sites arranged in a gradient of basicity. We reveal that Cu-Pt-Au MNCs supported on graphitized mesoporous carbon show catalytic activity that is 24 times greater than that of a commercially available Pt catalyst for aerobic oxidation of hydrocarbons. In addition, solvent-free aerobic oxidation of hydrocarbons to ketones at room temperature, using small amounts of a radical initiator, was achieved as a heterogeneous catalytic reaction for the first time. PMID:28782020

A technique to functionalize and self-assemble macroscopic nanoparticle-ligand monolayer films onto template-free substrates.

PubMed

Fontana, Jake; Spillmann, Christopher; Naciri, Jawad; Ratna, Banahalli R

2014-05-09

This protocol describes a self-assembly technique to create macroscopic monolayer films composed of ligand-coated nanoparticles. The simple, robust and scalable technique efficiently functionalizes metallic nanoparticles with thiol-ligands in a miscible water/organic solvent mixture allowing for rapid grafting of thiol groups onto the gold nanoparticle surface. The hydrophobic ligands on the nanoparticles then quickly phase separate the nanoparticles from the aqueous based suspension and confine them to the air-fluid interface. This drives the ligand-capped nanoparticles to form monolayer domains at the air-fluid interface. The use of water-miscible organic solvents is important as it enables the transport of the nanoparticles from the interface onto template-free substrates. The flow is mediated by a surface tension gradient and creates macroscopic, high-density, monolayer nanoparticle-ligand films. This self-assembly technique may be generalized to include the use of particles of different compositions, size, and shape and may lead to an efficient assembly method to produce low-cost, macroscopic, high-density, monolayer nanoparticle films for wide-spread applications.

Evaporation Behavior and Characterization of Eutectic Solvent and Ibuprofen Eutectic Solution.

PubMed

Phaechamud, Thawatchai; Tuntarawongsa, Sarun; Charoensuksai, Purin

2016-10-01

Liquid eutectic system of menthol and camphor has been reported as solvent and co-solvent for some drug delivery systems. However, surprisingly, the phase diagram of menthol-camphor eutectic has not been reported previously. The evaporation behavior, physicochemical, and thermal properties of this liquid eutectic and ibuprofen eutectic solution were characterized in this study. Differential scanning calorimetry (DSC) analysis indicated that a eutectic point of this system was near to 1:1 menthol/camphor and its eutectic temperature was -1°C. The solubility of ibuprofen in this eutectic was 282.11 ± 6.67 mg mL(-1) and increased the drug aqueous solubility fourfold. The shift of wave number from Fourier transform infrared spectroscopy (FTIR) indicated the hydrogen bonding of each compound in eutectic mixture. The weight loss from thermogravimetric analysis of menthol and camphor related to the evaporation and sublimation, respectively. Menthol demonstrated a lower apparent sublimation rate than camphor, and the evaporation rate of eutectic solvent was lower than the sublimation rate of camphor but higher than the evaporation of menthol. The evaporation rate of the ibuprofen eutectic solution was lower than that of the eutectic solvent because ibuprofen did not sublimate. This eutectic solvent prolonged the ibuprofen release with diffusion control. Thus, the beneficial information for thermal behavior and related properties of eutectic solvent comprising menthol-camphor and ibuprofen eutectic solution was attained successfully. The rather low evaporation of eutectic mixture will be beneficial for investigation and tracking the mechanism of transformation from nanoemulsion into nanosuspension in the further study using eutectic as oil phase.

A survey of extraction solvents in the forensic analysis of textile dyes.

PubMed

Groves, Ethan; Palenik, Christopher S; Palenik, Skip

2016-11-01

The characterization and identification of dyes in fibers can be used to provide investigative leads and strengthen associations between known and questioned items of evidence. The isolation of a dye from its matrix (e.g., a textile fiber) permits detailed characterization, comparison and, in some cases, identification using methods such as thin layer chromatography in conjunction with infrared and Raman spectroscopy. A survey of dye extraction publications reveals that pyridine:water (4:3) is among the most commonly cited extraction solvent across a range of fiber and dye chemistries. Here, the efficacy of this solvent system has been evaluated for the extraction of dyes from 172 commercially prevalent North American textile dyes. The evaluated population represents seven dye application classes, 18 chemical classes, and spans nine types of commercial textile fibers. The results of this survey indicate that ∼82% of the dyestuffs studied are extractable using this solvent system. The results presented here summarize the extraction efficacy by class and fiber type and illustrate that this solvent system is applicable to a wider variety of classes and fibers than previously indicated in the literature. While there is no universal solvent for fiber extraction, these results demonstrate that pyridine:water represents an excellent first step for extracting unknown dyes from questioned fibers in forensic casework. Copyright © 2016 Elsevier Ireland Ltd. All rights reserved.

Estimating system parameters for solvent-water and plant cuticle-water using quantum chemically estimated Abraham solute parameters.

PubMed

Liang, Yuzhen; Torralba-Sanchez, Tifany L; Di Toro, Dominic M

2018-04-18

Polyparameter Linear Free Energy Relationships (pp-LFERs) using Abraham system parameters have many useful applications. However, developing the Abraham system parameters depends on the availability and quality of the Abraham solute parameters. Using Quantum Chemically estimated Abraham solute Parameters (QCAP) is shown to produce pp-LFERs that have lower root mean square errors (RMSEs) of predictions for solvent-water partition coefficients than parameters that are estimated using other presently available methods. pp-LFERs system parameters are estimated for solvent-water, plant cuticle-water systems, and for novel compounds using QCAP solute parameters and experimental partition coefficients. Refitting the system parameter improves the calculation accuracy and eliminates the bias. Refitted models for solvent-water partition coefficients using QCAP solute parameters give better results (RMSE = 0.278 to 0.506 log units for 24 systems) than those based on ABSOLV (0.326 to 0.618) and QSPR (0.294 to 0.700) solute parameters. For munition constituents and munition-like compounds not included in the calibration of the refitted model, QCAP solute parameters produce pp-LFER models with much lower RMSEs for solvent-water partition coefficients (RMSE = 0.734 and 0.664 for original and refitted model, respectively) than ABSOLV (4.46 and 5.98) and QSPR (2.838 and 2.723). Refitting plant cuticle-water pp-LFER including munition constituents using QCAP solute parameters also results in lower RMSE (RMSE = 0.386) than that using ABSOLV (0.778) and QSPR (0.512) solute parameters. Therefore, for fitting a model in situations for which experimental data exist and system parameters can be re-estimated, or for which system parameters do not exist and need to be developed, QCAP is the quantum chemical method of choice.

Numerical Treatment of Stokes Solvent Flow and Solute-Solvent Interfacial Dynamics for Nonpolar Molecules.

PubMed

Sun, Hui; Zhou, Shenggao; Moore, David K; Cheng, Li-Tien; Li, Bo

2016-05-01

We design and implement numerical methods for the incompressible Stokes solvent flow and solute-solvent interface motion for nonpolar molecules in aqueous solvent. The balance of viscous force, surface tension, and van der Waals type dispersive force leads to a traction boundary condition on the solute-solvent interface. To allow the change of solute volume, we design special numerical boundary conditions on the boundary of a computational domain through a consistency condition. We use a finite difference ghost fluid scheme to discretize the Stokes equation with such boundary conditions. The method is tested to have a second-order accuracy. We combine this ghost fluid method with the level-set method to simulate the motion of the solute-solvent interface that is governed by the solvent fluid velocity. Numerical examples show that our method can predict accurately the blow up time for a test example of curvature flow and reproduce the polymodal (e.g., dry and wet) states of hydration of some simple model molecular systems.

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

PubMed

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

2016-07-22

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

Numerical Treatment of Stokes Solvent Flow and Solute-Solvent Interfacial Dynamics for Nonpolar Molecules

PubMed Central

Sun, Hui; Zhou, Shenggao; Moore, David K.; Cheng, Li-Tien; Li, Bo

2015-01-01

We design and implement numerical methods for the incompressible Stokes solvent flow and solute-solvent interface motion for nonpolar molecules in aqueous solvent. The balance of viscous force, surface tension, and van der Waals type dispersive force leads to a traction boundary condition on the solute-solvent interface. To allow the change of solute volume, we design special numerical boundary conditions on the boundary of a computational domain through a consistency condition. We use a finite difference ghost fluid scheme to discretize the Stokes equation with such boundary conditions. The method is tested to have a second-order accuracy. We combine this ghost fluid method with the level-set method to simulate the motion of the solute-solvent interface that is governed by the solvent fluid velocity. Numerical examples show that our method can predict accurately the blow up time for a test example of curvature flow and reproduce the polymodal (e.g., dry and wet) states of hydration of some simple model molecular systems. PMID:27365866

Thermodynamic Parameters of the Dissolution of 4-Hydroxy-L-Proline and L-Phenylalanine in Mixed Aqueous Solvents at 298 K

NASA Astrophysics Data System (ADS)

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

2018-01-01

The enthalpies of solution of 4-hydroxy-L-proline and L-phenylalanine in binary mixed aqueous solvents containing acetonitrile (AN), 1,4-dioxane (1,4-DO), or acetone (AC) at mole fractions of 0 to 0.25 are determined at T = 298.15 K via isothermal calorimetry. The standard enthalpies of solution (Δsol H°) and transfer (Δtr H°) of 4-hydroxy-L-proline and L-phenylalanine from water to mixed aqueous solvents are calculated using the experimental calorimetric data, as are the enthalpy coefficients of paired interactions ( h xy ) between the molecules of the investigated amino acids and the organic solvents. The effects the mixed aqueous solvent composition and the structure of the organic solvent molecules have on the enthalpies of solution and transfer for the investigated amino acids are considered. The correlation between the enthalpy of solution of the amino acids and the electron-donating properties of the organic solvents in the mixed aqueous solvent systems is established.

Toward the Application of the Maximum Entropy Production Principle to a Broader Range of Far From Equilibrium Dissipative Systems

NASA Astrophysics Data System (ADS)

Lineweaver, C. H.

2005-12-01

The principle of Maximum Entropy Production (MEP) is being usefully applied to a wide range of non-equilibrium processes including flows in planetary atmospheres and the bioenergetics of photosynthesis. Our goal of applying the principle of maximum entropy production to an even wider range of Far From Equilibrium Dissipative Systems (FFEDS) depends on the reproducibility of the evolution of the system from macro-state A to macro-state B. In an attempt to apply the principle of MEP to astronomical and cosmological structures, we investigate the problematic relationship between gravity and entropy. In the context of open and non-equilibrium systems, we use a generalization of the Gibbs free energy to include the sources of free energy extracted by non-living FFEDS such as hurricanes and convection cells. Redox potential gradients and thermal and pressure gradients provide the free energy for a broad range of FFEDS, both living and non-living. However, these gradients have to be within certain ranges. If the gradients are too weak, FFEDS do not appear. If the gradients are too strong FFEDS disappear. Living and non-living FFEDS often have different source gradients (redox potential gradients vs thermal and pressure gradients) and when they share the same gradient, they exploit different ranges of the gradient. In a preliminary attempt to distinguish living from non-living FFEDS, we investigate the parameter space of: type of gradient and steepness of gradient.

A combination strategy for extraction and isolation of multi-component natural products by systematic two-phase solvent extraction-(13)C nuclear magnetic resonance pattern recognition and following conical counter-current chromatography separation: Podophyllotoxins and flavonoids from Dysosma versipellis (Hance) as examples.

PubMed

Yang, Zhi; Wu, Youqian; Wu, Shihua

2016-01-29

Despite of substantial developments of extraction and separation techniques, isolation of natural products from natural resources is still a challenging task. In this work, an efficient strategy for extraction and isolation of multi-component natural products has been successfully developed by combination of systematic two-phase liquid-liquid extraction-(13)C NMR pattern recognition and following conical counter-current chromatography separation. A small-scale crude sample was first distributed into 9 systematic hexane-ethyl acetate-methanol-water (HEMWat) two-phase solvent systems for determination of the optimum extraction solvents and partition coefficients of the prominent components. Then, the optimized solvent systems were used in succession to enrich the hydrophilic and lipophilic components from the large-scale crude sample. At last, the enriched components samples were further purified by a new conical counter-current chromatography (CCC). Due to the use of (13)C NMR pattern recognition, the kinds and structures of major components in the solvent extracts could be predicted. Therefore, the method could collect simultaneously the partition coefficients and the structural information of components in the selected two-phase solvents. As an example, a cytotoxic extract of podophyllotoxins and flavonoids from Dysosma versipellis (Hance) was selected. After the systematic HEMWat system solvent extraction and (13)C NMR pattern recognition analyses, the crude extract of D. versipellis was first degreased by the upper phase of HEMWat system (9:1:9:1, v/v), and then distributed in the two phases of the system of HEMWat (2:8:2:8, v/v) to obtain the hydrophilic lower phase extract and lipophilic upper phase extract, respectively. These extracts were further separated by conical CCC with the HEMWat systems (1:9:1:9 and 4:6:4:6, v/v). As results, total 17 cytotoxic compounds were isolated and identified. In general, whole results suggested that the strategy was very efficient for the systematic extraction and isolation of biological active components from the complex biomaterials. Copyright © 2016 Elsevier B.V. All rights reserved.

Protein-style dynamical transition in a non-biological polymer and a non-aqueous solvent

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

Mamontov, E.; Sharma, V. K.; Borreguero, J. M.

Using neutron scattering and molecular dynamics simulation, techniques most often associated with protein dynamical transition studies, we have investigated the microscopic dynamics of one of the most common polymers, polystyrene, which was exposed to toluene vapor, mimicking the process of protein hydration from water vapor. Polystyrene with adsorbed toluene is an example of a solvent-solute system, which, unlike biopolymers, is anhydrous and lacks hydrogen bonding. Nevertheless, it exhibits the essential traits of the dynamical transition in biomolecules, such as a specific dependence of the microscopic dynamics of both solvent and host on the temperature and the amount of solvent adsorbed.more » Ultimately, we conclude that the protein dynamical transition is a manifestation of a universal solvent-solute dynamical relationship, which is not specific to either biomolecules as solute, or aqueous media as solvent, or even a particular type of interactions between solvent and solute.« less

Protein-style dynamical transition in a non-biological polymer and a non-aqueous solvent

DOE PAGES

Mamontov, E.; Sharma, V. K.; Borreguero, J. M.; ...

2016-03-15

Using neutron scattering and molecular dynamics simulation, techniques most often associated with protein dynamical transition studies, we have investigated the microscopic dynamics of one of the most common polymers, polystyrene, which was exposed to toluene vapor, mimicking the process of protein hydration from water vapor. Polystyrene with adsorbed toluene is an example of a solvent-solute system, which, unlike biopolymers, is anhydrous and lacks hydrogen bonding. Nevertheless, it exhibits the essential traits of the dynamical transition in biomolecules, such as a specific dependence of the microscopic dynamics of both solvent and host on the temperature and the amount of solvent adsorbed.more » Ultimately, we conclude that the protein dynamical transition is a manifestation of a universal solvent-solute dynamical relationship, which is not specific to either biomolecules as solute, or aqueous media as solvent, or even a particular type of interactions between solvent and solute.« less

Method for destroying halocarbon compositions using a critical solvent

DOEpatents

Ginosar, Daniel M.; Fox, Robert V.; Janikowski, Stuart K.

2006-01-10

A method for destroying halocarbons. Halocarbon materials are reacted in a dehalogenation process wherein they are combined with a solvent in the presence of a catalyst. A hydrogen-containing solvent is preferred which functions as both a solvating agent and hydrogen donor. To augment the hydrogen donation capacity of the solvent if needed (or when non-hydrogen-containing solvents are used), a supplemental hydrogen donor composition may be employed. In operation, at least one of the temperature and pressure of the solvent is maintained near, at, or above a critical level. For example, the solvent may be in (1) a supercritical state; (2) a state where one of the temperature or pressure thereof is at or above critical; or (3) a state where at least one of the temperature and pressure thereof is near-critical. This system provides numerous benefits including improved reaction rates, efficiency, and versatility.

Extracting organic matter on Mars: A comparison of methods involving subcritical water, surfactant solutions and organic solvents

NASA Astrophysics Data System (ADS)

Luong, Duy; Court, Richard W.; Sims, Mark R.; Cullen, David C.; Sephton, Mark A.

2014-09-01

The first step in many life detection protocols on Mars involves attempts to extract or isolate organic matter from its mineral matrix. A number of extraction options are available and include heat and solvent assisted methods. Recent operations on Mars indicate that heating samples can cause the loss or obfuscation of organic signals from target materials, raising the importance of solvent-based systems for future missions. Several solvent types are available (e.g. organic solvents, surfactant based solvents and subcritical water extraction) but a comparison of their efficiencies in Mars relevant materials is missing. We have spiked the well characterised Mars analogue material JSC Mars-1 with a number of representative organic standards. Extraction of the spiked JSC Mars-1 with the three solvent methods provides insights into the relative efficiency of these methods and indicates how they may be used on future Mars missions.

An extensible framework for capturing solvent effects in computer generated kinetic models.

PubMed

Jalan, Amrit; West, Richard H; Green, William H

2013-03-14

Detailed kinetic models provide useful mechanistic insight into a chemical system. Manual construction of such models is laborious and error-prone, which has led to the development of automated methods for exploring chemical pathways. These methods rely on fast, high-throughput estimation of species thermochemistry and kinetic parameters. In this paper, we present a methodology for extending automatic mechanism generation to solution phase systems which requires estimation of solvent effects on reaction rates and equilibria. The linear solvation energy relationship (LSER) method of Abraham and co-workers is combined with Mintz correlations to estimate ΔG(solv)°(T) in over 30 solvents using solute descriptors estimated from group additivity. Simple corrections are found to be adequate for the treatment of radical sites, as suggested by comparison with known experimental data. The performance of scaled particle theory expressions for enthalpic-entropic decomposition of ΔG(solv)°(T) is also presented along with the associated computational issues. Similar high-throughput methods for solvent effects on free-radical kinetics are only available for a handful of reactions due to lack of reliable experimental data, and continuum dielectric calculations offer an alternative method for their estimation. For illustration, we model liquid phase oxidation of tetralin in different solvents computing the solvent dependence for ROO• + ROO• and ROO• + solvent reactions using polarizable continuum quantum chemistry methods. The resulting kinetic models show an increase in oxidation rate with solvent polarity, consistent with experiment. Further work needed to make this approach more generally useful is outlined.

Small-Molecule Organic Photovoltaic Modules Fabricated via Halogen-Free Solvent System with Roll-to-Roll Compatible Scalable Printing Method.

PubMed

Heo, Youn-Jung; Jung, Yen-Sook; Hwang, Kyeongil; Kim, Jueng-Eun; Yeo, Jun-Seok; Lee, Sehyun; Jeon, Ye-Jin; Lee, Donmin; Kim, Dong-Yu

2017-11-15

For the first time, the photovoltaic modules composed of small molecule were successfully fabricated by using roll-to-roll compatible printing techniques. In this study, blend films of small molecules, BTR and PC 71 BM were slot-die coated using a halogen-free solvent system. As a result, high efficiencies of 7.46% and 6.56% were achieved from time-consuming solvent vapor annealing (SVA) treatment and roll-to-roll compatible solvent additive approaches, respectively. After successful verification of our roll-to-roll compatible method on small-area devices, we further fabricated large-area photovoltaic modules with a total active area of 10 cm 2 , achieving a power conversion efficiency (PCE) of 4.83%. This demonstration of large-area photovoltaic modules through roll-to-roll compatible printing methods, even based on a halogen-free solvent, suggests the great potential for the industrial-scale production of organic solar cells (OSCs).

Simultaneous measurements of absorption spectrum and refractive index in a microfluidic system.

PubMed

Helseth, Lars Egil

2012-02-13

The characterization of dyes in various solvents requires determination of the absorption spectrum of the dye as well as the refractive index of the solvent. Typically, the refractive index of the solvent and the absorption spectrum of the solute are measured using separate experimental setups where significant liquid volumes are required. In this work the first optical measurement system that is able to do simultaneous measurements of the refractive index of the solvent and the spectral properties of the solute in a microscopic volume is presented. The laser dye Rhodamine 6G in glycerol is investigated, and the refractive index of the solution is monitored using the interference pattern of the light scattered off the channel, while its spectral properties is found by monitoring reflected light from the channel.

Alternative Green Solvents Project

NASA Technical Reports Server (NTRS)

Maloney, Phillip R.

2012-01-01

Necessary for safe and proper functioning of equipment. Mainly halogenated solvents. Tetrachloride, Trichloroethylene (TCE), CFC-113. No longer used due to regulatory/safety concerns. Precision Cleaning at KSC: Small % of total parts. Used for liquid oxygen (LOX) systems. Dual solvent process. Vertrel MCA (decafluoropentane (DFP) and trons-dichloroethylene) HFE-7100. DFP has long term environmental concerns. Project Goals: a) Identify potential replacements. b) 22 wet chemical processes. c) 3 alternative processes. d) Develop test procedures. e) Contamination and cleaning. f) Analysis. g) Use results to recommend alternative processes. Conclusions: a) No alternative matched Vertrel in this study. b) No clear second place solvent. c) Hydrocarbons- easy; Fluorinated greases- difficult. d) Fluorinated component may be needed in replacement solvent. e) Process may need to make up for shortcoming of the solvent. f) Plasma and SCC02 warrant further testing.

AFM fluid delivery/liquid extraction surface sampling/electrostatic spray cantilever probe

DOEpatents

Van Berkel, Gary J.

2015-06-23

An electrospray system comprises a liquid extraction surface sampling probe. The probe comprises a probe body having a liquid inlet and a liquid outlet, and having a liquid extraction tip. A solvent delivery conduit is provided for receiving solvent liquid from the liquid inlet and delivering the solvent liquid to the liquid extraction tip. An open liquid extraction channel extends across an exterior surface of the probe body from the liquid extraction tip to the liquid outlet. An electrospray emitter tip is in liquid communication with the liquid outlet of the liquid extraction surface sampling probe. A system for analyzing samples, a liquid junction surface sampling system, and a method of analyzing samples are also disclosed.

Water as a Solvent for Life

NASA Technical Reports Server (NTRS)

Pohorille, Andrew; Pratt, Lawrence R.

2015-01-01

"Follow the water" is our basic strategy in searching for life in the universe. The universality of water as the solvent for living systems is usually justified by arguing that water supports the rich organic chemistry that seeds life, but alternative chemistries are possible in other organic solvents. Here, other, essential criteria for life that have not been sufficiently considered so far, will be discussed.

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

PubMed

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

2017-02-02

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

Diffusional Motion of Redox Centers in Carbonate Electrolytes

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

Han, Kee Sung; Rajput, Nav Nidhi; Wei, Xiaoliang

2014-09-14

Ferrocene (Fc) and N-(ferrocenylmethyl)-N,N-dimethyl-N-ethylammonium bistrifluoromethyl-sulfonimide (Fc1N112-TFSI) were dissolved in carbonate solvents and self diffusion coefficents (D) of solutes and solvents were measured by 1H and 19F pulsed field gradient (PFG) nuclear magnetic resonance (NMR) spectroscopy. The organic solvents were propylene carbonate (PC), ethyl methyl carbonate (EMC) and a ternary mixture that also includes ethylene carbonate (EC). Results from NMR studies over the temperature range of 0-50 °C and for various concentrations (0.25 - 1.7 M) of Fc1N112-TFSI are compared to values of D simulated with classical molecular dynamics (MD). The measured self-diffusion coefficients gradually decreased as the Fc1N112-TFSI concentration increasedmore » in all solvents. Since the peaks for the two ions (Fc1N212 and TFSI) are separated in one-dimensional NMR spectra, separate diffusion coefficients could be measured and DTFSI is larger than DFc1N112 in all samples measured. The EC, PC and EMC have the same D in the neat solvent mixture and when Fc is dissolved in EC/PC/EMC at a concentration of 0.2 M, probably due to the interactions between common carbonyl structures within EC, PC and EMC. A difference in D (DPC < DEC < DEMC), and both a higher Ea for translational motion and higher effective viscosity for PC in the mixture containing Fc1N112-TFSI reflect the interaction between PC and Fc1N112+, which is a relatively stronger interaction than that between Fc1N112+ and other solvent species. In the EC/PC/EMC solution that is saturated with Fc1N112-TFSI, we find that DPC = DEC = DEMC and Fc1N112+ and all components of the EC/PC/EMC solution have the same Ea for translational motion, while the ratio DEC/PC/EMC/DFc1N112+ is approximately 3. These results reflect the lack of available free volume for independent diffusion in the saturated solution. The Fc1N112+ transference numbers lie around 0.4 and increases slightly as the temperature is increased in the PC and EMC solvents. The trends observed for D from simulations are in good agreement with experimental results and provide molecular level understanding of the solvation structure of Fc1N112-TFSI dissolved in EC/PC/EMC.« less

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

Han, Kee Sung; Rajput, Nav Nidhi; Persson, Kristin A.

Ferrocene (Fc) and N-(ferrocenylmethyl)-N,N-dimethyl-N-ethylammonium bistrifluoromethyl-sulfonimide (Fc1N112-TFSI) were dissolved in carbonate solvents and self-diffusion coefficients (D) of solutes and solvents were measured by {sup 1}H and {sup 19}F pulsed field gradient nuclear magnetic resonance (NMR) spectroscopy. The organic solvents were propylene carbonate (PC), ethyl methyl carbonate (EMC), and a ternary mixture that also includes ethylene carbonate (EC). Results from NMR studies over the temperature range of 0–50 °C and for various concentrations (0.25–1.7 M) of Fc1N112-TFSI are compared to values of D simulated with classical molecular dynamics (MD). The measured self-diffusion coefficients gradually decreased as the Fc1N112-TFSI concentration increased in allmore » solvents. Since TFSI{sup −} has fluoromethyl groups (CF{sub 3}), D{sub TFSI} could be measured separately and the values found are larger than those for D{sub Fc1N112} in all samples measured. The EC, PC, and EMC have the same D in the neat solvent mixture and when Fc is dissolved in EC/PC/EMC at a concentration of 0.2 M, probably due to the interactions between common carbonyl structures within EC, PC, and EMC. A difference in D (D{sub PC} < D{sub EC} < D{sub EMC}), and both a higher E{sub a} for translational motion and higher effective viscosity for PC in the mixture containing Fc1N112-TFSI reflect the interaction between PC and Fc1N112{sup +}, which is a relatively stronger interaction than that between Fc1N112{sup +} and other solvent species. In the EC/PC/EMC solution that is saturated with Fc1N112-TFSI, we find that D{sub PC} = D{sub EC} = D{sub EMC} and Fc1N112{sup +} and all components of the EC/PC/EMC solution have the same E{sub a} for translational motion, while the ratio D{sub EC/PC/EMC}/D{sub Fc1N112} is approximately 3. These results reflect the lack of available free volume for independent diffusion in the saturated solution. The Fc1N112{sup +} transference numbers lie around 0.4 and increase slightly as the temperature is increased in the PC and EMC solvents. The trends observed for D from simulations are in good agreement with experimental results and provide molecular level understanding of the solvation structure of Fc1N112-TFSI dissolved in EC/PC/EMC.« less

Can solvent induced surface modifications applied to screen-printed platforms enhance their electroanalytical performance?

PubMed

Blanco, Elias; Foster, Christopher W; Cumba, Loanda R; do Carmo, Devaney R; Banks, Craig E

2016-04-25

In this paper the effect of solvent induced chemical surface enhancements upon graphitic screen-printed electrodes (SPEs) is explored. Previous literature has indicated that treating the working electrode of a SPE with the solvent N,N-dimethylformamide (DMF) offers improvements within the electroanalytical response, resulting in a 57-fold increment in the electrode surface area compared to their unmodified counterparts. The protocol involves two steps: (i) the SPE is placed into DMF for a selected time, and (ii) it is cured in an oven at a selected time and temperature. Beneficial electroanalytical outputs are reported to be due to the increased surface area attributed to the binder within the bulk surface of the SPEs dissolving out during the immersion step (step i). We revisit this exciting concept and explore these solvent induced chemical surface enhancements using edge- and basal-plane like SPEs and a new bespoke SPE, utilising the solvent DMF and explore, in detail, the parameters utilised in steps (i) and (ii). The electrochemical performance following steps (i) and (ii) is evaluated using the outer-sphere redox probe hexaammineruthenium(iii) chloride/0.1 M KCl, where it is found that the largest improvement is obtained using DMF with an immersion time of 10 minutes and a curing time of 30 minutes at 100 °C. Solvent induced chemical surface enhancement upon the electrochemical performance of SPEs is also benchmarked in terms of their electroanalytical sensing of NADH (dihydronicotinamide adenine dinucleotide reduced form) and capsaicin both of which are compared to their unmodified SPE counterparts. In both cases, it is apparent that a marginal improvement in the electroanalytical sensitivity (i.e. gradient of calibration plots) of 1.08-fold and 1.38-fold are found respectively. Returning to the original exciting concept, interestingly it was found that when a poor experimental technique was employed, only then significant increases within the working electrode area are evident. In this case, the insulating layer that defines the working electrode surface, which was not protected from the solvent (step (i)) creates cracks within the insulating layer exposing the underlying carbon connections and thus increasing the electrode area by an unknown quantity. We infer that the origin of the response reported within the literature, where an extreme increase in the electrochemical surface area (57-fold) was reported, is unlikely to be solely due to the binder dissolving but rather poor experimental control over step (i).

Enzymes from solvent-tolerant microbes: useful biocatalysts for non-aqueous enzymology.

PubMed

Gupta, Anshu; Khare, S K

2009-01-01

Solvent-tolerant microbes are a newly emerging class that possesses the unique ability to thrive in the presence of organic solvents. Their enzymes adapted to mediate cellular and metabolic processes in a solvent-rich environment and are logically stable in the presence of organic solvents. Enzyme catalysis in non-aqueous/low-water media is finding increasing applications for the synthesis of industrially important products, namely peptides, esters, and other trans-esterification products. Solvent stability, however, remains a prerequisite for employing enzymes in non-aqueous systems. Enzymes, in general, get inactivated or give very low rates of reaction in non-aqueous media. Thus, early efforts, and even some recent ones, have aimed at stabilization of enzymes in organic media by immobilization, surface modifications, mutagenesis, and protein engineering. Enzymes from solvent-tolerant microbes appear to be the choicest source for studying solvent-stable enzymes because of their unique ability to survive in the presence of a range of organic solvents. These bacteria circumvent the solvent's toxic effects by virtue of various adaptations, e.g. at the level of the cytoplasmic membrane, by degradation and transformation of solvents, and by active excretion of solvents. The recent screening of these exotic microbes has generated some naturally solvent-stable proteases, lipases, cholesterol oxidase, cholesterol esterase, cyclodextrin glucanotransferase, and other important enzymes. The unique properties of these novel biocatalysts have great potential for applications in non-aqueous enzymology for a range of industrial processes.

Radiation-induced polymerization of glass-forming systems. V. Initial polymerization rate in binary glass-forming systems

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

Kaetsu, Isao; Okubo, Hiroshi; Ito, Akihiko

1973-06-01

The radiation-induced polymerization of binary systems consisting of glass-forming monomer and glass-forming solvent in supercooled phase was studied. The initial polymerization rates were markedly affected by T/sub g/ (glass transition temperature) and T/sub v/ of the system (30-50 deg C higher than T/sub g/), which are functions of the composition. The composition and temperature dependence of initial polymerization rate in binary glass-forming systems were much affected by homogeneity of the polymerization system and the T of the glass- forming solvent. The composition and temperature dependences in the glycidyl methacrylate --triacetin system as a typical homogeneous polymerization system were studied inmore » detail, and the polymerizations of hydroxyethyl methacrylate triacetln and hydroxyethyl methacrylate --isoamyl acetate systems were studied for the heterogeneous polymerization systems; the former illustrates the combination of lower T/sub g/ monomer and higher T/sub g/ solvent and the latter typifies a system consisting of higher T/sub g/ monomer and lower T/sub g/ solvent. All experimental results for the composition and temperature dependence of initial polymerization rate in binary glass-forming systems could be explained by considering the product of the effect of the physical effect relating to T/sub v/ and T/sub g/ of the system and the effect of composition in normal solution polymerization at higher temperature, which was also the product of a dilution effect and a chemical or physical acceleration effect. (auth)« less

A RP-LC method with evaporative light scattering detection for the assay of simethicone in pharmaceutical formulations.

PubMed

Moore, Douglas E; Liu, Tina X; Miao, William G; Edwards, Alison; Elliss, Russell

2002-09-05

A reversed-phase liquid chromatographic method has been developed and validated for the determination of the polydimethylsiloxane (PDMS) component of Simethicone, which is used as an anti-foaming agent in pharmaceutical formulations. The method involves acidification to neutralise antacid components of the formulation, then a single extraction of the PDMS with dichloromethane. This is followed by separation with a reversed-phase column using an acetonitrile-chloroform solvent gradient, and quantification by an evaporative light scattering detector. An assay precision of 3% was achieved in intraday and interday determinations. No interference was found from the aluminium and magnesium hydroxide components of antacid formulations.

Environmental stress cracking of polymers

NASA Technical Reports Server (NTRS)

Mahan, K. I.

1980-01-01

A two point bending method for use in studying the environmental stress cracking and crazing phenomena is described and demonstrated for a variety of polymer/solvent systems. Critical strain values obtained from these curves are reported for various polymer/solvent systems including a considerable number of systems for which critical strain values have not been previously reported. Polymers studied using this technique include polycarbonate (PC), ABS, high impact styrene (HIS), polyphenylene oxide (PPO), and polymethyl methacrylate (PMMA). Critical strain values obtained using this method compared favorably with available existing data. The major advantage of the technique is the ability to obtain time vs. strain curves over a short period of time. The data obtained suggests that over a short period of time the transition in most of the polymer solvent systems is more gradual than previously believed.

Effects of solvents and salt on the thermal stability of lithiated graphite used in lithium ion battery.

PubMed

Wang, Qingsong; Sun, Jinhua; Chen, Chunhua

2009-08-15

The thermal stability of lithiated graphite in the presence of solvents, electrolytes and LiPF(6) salt was studied using C80 micro-calorimeter. The presence of cyclic carbonates or linear carbonates increases the activity of Li(x)C(6)-solvent coexisting system, especially for the Li(x)C(6)-linear carbonates one. LiPF(6) was detected that it increases the activity greatly of its coexisting system with lithiated graphite. The coexisting system of Li(x)C(6) with the electrolyte of LiPF(6)/ethylene carbonate+diethyl carbonate shows less thermal stability, which is attributed to the activity between diethyl carbonate and Li(x)C(6). This also agrees with the experiment result of Li(x)C(6)-diethyl carbonate coexisting system.

Continuous extraction of organic materials from water

USGS Publications Warehouse

Goldberg, M.C.; DeLong, L.; Kahn, L.

1971-01-01

A continuous liquid solvent extractor, designed to utilize organic solvents that are heavier than water, is described. The extractor is capable of handling input rates up to 2 liters per hour and has a 500-ml. extractant capacity. Extraction efficiency is dependent upon the p-value, the two solvent ratios, rate of flow of the aqueous phase, and rate of reflux of the organic phase. Extractors can be serially coupled to increase extraction efficiency and, when coupled with a lighter-than-water extractor, the system will allow the use of any immiscible solvent.

Process for producing fuel grade ethanol by continuous fermentation, solvent extraction and alcohol separation

DOEpatents

Tedder, Daniel W.

1985-05-14

Alcohol substantially free of water is prepared by continuously fermenting a fermentable biomass feedstock in a fermentation unit, thereby forming an aqueous fermentation liquor containing alcohol and microorganisms. Continuously extracting a portion of alcohol from said fermentation liquor with an organic solvent system containing an extractant for said alcohol, thereby forming an alcohol-organic solvent extract phase and an aqueous raffinate. Said alcohol is separated from said alcohol-organic solvent phase. A raffinate comprising microorganisms and unextracted alcohol is returned to the fermentation unit.

Two novel solvent system compositions for protected synthetic peptide purification by centrifugal partition chromatography.

PubMed

Amarouche, Nassima; Giraud, Matthieu; Forni, Luciano; Butte, Alessandro; Edwards, F; Borie, Nicolas; Renault, Jean-Hugues

2014-04-11

Protected synthetic peptide intermediates are often hydrophobic and not soluble in most common solvents. They are thus difficult to purify by preparative reversed-phase high-performance liquid chromatography (RP-HPLC), usually used for industrial production. It is then challenging to develop alternative chromatographic purification processes. Support-free liquid-liquid chromatographic techniques, including both hydrostatic (centrifugal partition chromatography or CPC) and hydrodynamic (counter-current chromatography or CCC) devices, are mainly involved in phytochemical studies but have also been applied to synthetic peptide purification. In this framework, two new biphasic solvent system compositions covering a wide range of polarity were developed to overcome solubility problems mentioned above. The new systems composed of heptane/tetrahydrofuran/acetonitrile/dimethylsulfoxide/water and heptane/methyl-tetrahydrofuran/N-methylpyrrolidone/water were efficiently used for the CPC purification of a 39-mer protected exenatide (Byetta®) and a 8-mer protected peptide intermediate of bivalirudin (Angiox®) synthesis. Phase compositions of the different biphasic solvent systems were determined by (1)H nuclear magnetic resonance. Physico-chemical properties including viscosity, density and interfacial tension of these biphasic systems are also described. Copyright © 2014 Elsevier B.V. All rights reserved.

On the relation between Marcus theory and ultrafast spectroscopy of solvation kinetics

NASA Astrophysics Data System (ADS)

Roy, Santanu; Galib, Mirza; Schenter, Gregory K.; Mundy, Christopher J.

2018-01-01

The phenomena of solvent exchange control the process of solvating ions, protons, and charged molecules. Building upon our extension of Marcus' philosophy of electron transfer, we provide a new perspective of ultrafast solvent exchange mechanism around ions measurable by two-dimensional infrared (2DIR) spectroscopy. In this theory, solvent rearrangement drives an ion-bound water to an activated state of higher coordination number, triggering ion-water separation that leads to the solvent-bound state of the water molecule. This ion-bound to solvent-bound transition rate for a BF4--water system is computed using ab initio molecular dynamics and Marcus theory, and is found to be in excellent agreement with the 2DIR measurement.

Effect of HEH[EHP] impurities on the ALSEP solvent extraction process

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

Holfeltz, Vanessa E.; Campbell, Emily L.; Peterman, Dean R.

In solvent extraction processes, organic phase impurities can negatively impact separation factors, hydrolytic performance, and overall system robustness. This affects the process-level viability of a separation concept and necessitates knowledge of the behavior and mechanisms to control impurities in the solvent. The most widespread way through which impurities are introduced into a system is through impure extractants and/or diluents used to prepare the solvent, and often development of new purification schemes to achieve the desired level of purity is needed. In this work, the acidic extractant, 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester (HEH[EHP])—proposed for application in extractive processes aimed at separating trivalentmore » minor actinides from lanthanides and other fission products—is characterized with respect to its common impurities and their impact on Am(III) stripping in the Actinide Lanthanide SEParation (ALSEP) system. To control impurities in HEH[EHP], existing purification technologies commonly applied for the acidic organophosphorus reagents are reviewed, and a new method specific to HEH[EHP] purification is presented.« less

Elucidating structural characteristics of biomass using solution-state 2 D NMR with a mixture of deuterated dimethylsulfoxide and hexamethylphosphoramide

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

Pu, Yunqiao; Ragauskas, Arthur J.; Yoo, Chang Geun

In recent developments of NMR methods for characterization of lignocellulosic biomass allow improved understanding of plant cell-wall structures with minimal deconstruction and modification of biomass. This study introduces a new NMR solvent system composed of dimethylsulfoxide (DMSO- d 6) and hexamethylphosphoramide (HMPA- d 18). HMPA as a co-solvent enhanced swelling and mobility of the biomass samples; thereby it allowed enhancing signals of NMR spectra. Moreover, the structural information of biomass was successfully analyzed by the proposed NMR solvent system (DMSO- d 6/HMPA-d 18; 4:1, v/v) with different biomass. The proposed bi-solvent system does not require derivatization or isolation of biomass,more » facilitating a facile sample preparation and involving with no signals overlapping with biomass peaks. Furthermore, it also allows analyzing biomass with a room-temperature NMR probe instead of cryo-probes, which are traditionally used for enhancing signal intensities.« less

Elucidating structural characteristics of biomass using solution-state 2 D NMR with a mixture of deuterated dimethylsulfoxide and hexamethylphosphoramide

DOE PAGES

Pu, Yunqiao; Ragauskas, Arthur J.; Yoo, Chang Geun; ...

2016-04-26

In recent developments of NMR methods for characterization of lignocellulosic biomass allow improved understanding of plant cell-wall structures with minimal deconstruction and modification of biomass. This study introduces a new NMR solvent system composed of dimethylsulfoxide (DMSO- d 6) and hexamethylphosphoramide (HMPA- d 18). HMPA as a co-solvent enhanced swelling and mobility of the biomass samples; thereby it allowed enhancing signals of NMR spectra. Moreover, the structural information of biomass was successfully analyzed by the proposed NMR solvent system (DMSO- d 6/HMPA-d 18; 4:1, v/v) with different biomass. The proposed bi-solvent system does not require derivatization or isolation of biomass,more » facilitating a facile sample preparation and involving with no signals overlapping with biomass peaks. Furthermore, it also allows analyzing biomass with a room-temperature NMR probe instead of cryo-probes, which are traditionally used for enhancing signal intensities.« less

Bio-oil extraction of Jatropha curcas with ionic liquid co-solvent: Fate of biomass protein.

PubMed

Severa, Godwin; Edwards, Melisa; Cooney, Michael J

2017-02-01

The fate of oil-seed biomass protein has been tracked through all steps of a multi-phase extraction process using an ionic liquid based co-solvent system previously demonstrated to extract bio-oil and phorbol esters and to recover fermentable sugars from Jatropha oil seed. These analyses, however, did not address the fate of biomass protein. This work demonstrated that the majority of protein (∼86%) tracked with the biomass with the balance lost to co-solvent (∼12%) and methanol (∼2%) washes. A significant portion of the ionic liquid remained with the treated biomass and required aggressive methanol washes to recover. A system analysis showed a net-positive energy balance and thus the potential of this system to produce both bio-oil and protein-rich toxin-free biomass. While these results further support Jatropha as an oil seed crop, the additional costs of solvent recovery will need to be addressed if commercialization is to be realized. Copyright © 2016 Elsevier Ltd. All rights reserved.

Elucidating Structural Characteristics of Biomass using Solution-State 2 D NMR with a Mixture of Deuterated Dimethylsulfoxide and Hexamethylphosphoramide.

PubMed

Yoo, Chang Geun; Pu, Yunqiao; Li, Mi; Ragauskas, Arthur J

2016-05-23

Recent developments of NMR methods for characterization of lignocellulosic biomass allow improved understanding of plant cell-wall structures with minimal deconstruction and modification of biomass. This study introduces a new NMR solvent system composed of dimethylsulfoxide (DMSO-d6 ) and hexamethylphosphoramide (HMPA-d18 ). HMPA as a co-solvent enhanced swelling and mobility of the biomass samples; thereby it allowed enhancing signals of NMR spectra. The structural information of biomass was successfully analyzed by the proposed NMR solvent system (DMSO-d6 /HMPA-d18 ; 4:1, v/v) with different biomass. The proposed bi-solvent system does not require derivatization or isolation of biomass, facilitating a facile sample preparation and involving with no signals overlapping with biomass peaks. It also allows analyzing biomass with a room-temperature NMR probe instead of cryo-probes, which are traditionally used for enhancing signal intensities. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Protein-solvent preferential interactions, protein hydration, and the modulation of biochemical reactions by solvent components.

PubMed

Timasheff, Serge N

2002-07-23

Solvent additives (cosolvents, osmolytes) modulate biochemical reactions if, during the course of the reaction, there is a change in preferential interactions of solvent components with the reacting system. Preferential interactions can be expressed in terms of preferential binding of the cosolvent or its preferential exclusion (preferential hydration). The driving force is the perturbation by the protein of the chemical potential of the cosolvent. It is shown that the measured change of the amount of water in contact with protein during the course of the reaction modulated by an osmolyte is a change in preferential hydration that is strictly a measure of the cosolvent chemical potential perturbation by the protein in the ternary water-protein-cosolvent system. It is not equal to the change in water of hydration, because water of hydration is a reflection strictly of protein-water forces in a binary system. There is no direct relation between water of preferential hydration and water of hydration.

Effective recovery of poly-β-hydroxybutyrate (PHB) biopolymer from Cupriavidus necator using a novel and environmentally friendly solvent system.

PubMed

Fei, Tao; Cazeneuve, Stacy; Wen, Zhiyou; Wu, Lei; Wang, Tong

2016-05-01

This work demonstrates a significant advance in bioprocessing for a high-melting lipid polymer. A novel and environmental friendly solvent mixture, acetone/ethanol/propylene carbonate (A/E/P, 1:1:1 v/v/v) was identified for extracting poly-hydroxybutyrate (PHB), a high-value biopolymer, from Cupriavidus necator. A set of solubility curves of PHB in various solvents was established. PHB recovery of 85% and purity of 92% were obtained from defatted dry biomass (DDB) using A/E/P. This solvent mixture is compatible with water, and from non-defatted wet biomass, PHB recovery of 83% and purity of 90% were achieved. Water and hexane were evaluated as anti-solvents to assist PHB precipitation, and hexane improved recovery of PHB from biomass to 92% and the purity to 93%. A scale-up extraction and separation reactor was designed, built and successfully tested. Properties of PHB recovered were not significantly affected by the extraction solvent and conditions, as shown by average molecular weight (1.4 × 10(6) ) and melting point (175.2°C) not being different from PHB extracted using chloroform. Therefore, this biorenewable solvent system was effective and versatile for extracting PHB biopolymers. © 2016 American Institute of Chemical Engineers Biotechnol. Prog., 32:678-685, 2016. © 2016 American Institute of Chemical Engineers.

Low density microcellular foams

DOEpatents

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

1985-10-02

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

Effect of ionization suppression by trace impurities in mobile phase water on the accuracy of quantification by high-performance liquid chromatography/mass spectrometry.

PubMed

Herath, H M D R; Shaw, P N; Cabot, P; Hewavitharana, A K

2010-06-15

The high-performance liquid chromatography (HPLC) column is capable of enrichment/pre-concentration of trace impurities in the mobile phase during the column equilibration, prior to sample injection and elution. These impurities elute during gradient elution and result in significant chromatographic peaks. Three types of purified water were tested for their impurity levels, and hence their performances as mobile phase, in HPLC followed by total ion current (TIC) mode of MS. Two types of HPLC-grade water produced 3-4 significant peaks in solvent blanks while LC/MS-grade water produced no peaks (although peaks were produced by LC/MS-grade water also after a few days of standing). None of the three waters produced peaks in HPLC followed by UV-Vis detection. These peaks, if co-eluted with analyte, are capable of suppressing or enhancing the analyte signal in a MS detector. As it is not common practice to run solvent blanks in TIC mode, when quantification is commonly carried out using single ion monitoring (SIM) or single or multiple reaction monitoring (SRM or MRM), the effect of co-eluting impurities on the analyte signal and hence on the accuracy of the results is often unknown to the analyst. Running solvent blanks in TIC mode, regardless of the MS mode used for quantification, is essential in order to detect this problem and to take subsequent precautions. Copyright (c) 2010 John Wiley & Sons, Ltd.

Remediation of Chlorinated Solvent Plumes Using In-Situ Air Sparging—A 2-D Laboratory Study

PubMed Central

Adams, Jeffrey A.; Reddy, Krishna R.; Tekola, Lue

2011-01-01

In-situ air sparging has evolved as an innovative technique for soil and groundwater remediation impacted with volatile organic compounds (VOCs), including chlorinated solvents. These may exist as non-aqueous phase liquid (NAPL) or dissolved in groundwater. This study assessed: (1) how air injection rate affects the mass removal of dissolved phase contamination, (2) the effect of induced groundwater flow on mass removal and air distribution during air injection, and (3) the effect of initial contaminant concentration on mass removal. Dissolved-phase chlorinated solvents can be effectively removed through the use of air sparging; however, rapid initial rates of contaminant removal are followed by a protracted period of lower removal rates, or a tailing effect. As the air flow rate increases, the rate of contaminant removal also increases, especially during the initial stages of air injection. Increased air injection rates will increase the density of air channel formation, resulting in a larger interfacial mass transfer area through which the dissolved contaminant can partition into the vapor phase. In cases of groundwater flow, increased rates of air injection lessened observed downward contaminant migration effect. The air channel network and increased air saturation reduced relative hydraulic conductivity, resulting in reduced groundwater flow and subsequent downgradient contaminant migration. Finally, when a higher initial TCE concentration was present, a slightly higher mass removal rate was observed due to higher volatilization-induced concentration gradients and subsequent diffusive flux. Once concentrations are reduced, a similar tailing effect occurs. PMID:21776228

Remediation of chlorinated solvent plumes using in-situ air sparging--a 2-D laboratory study.

PubMed

Adams, Jeffrey A; Reddy, Krishna R; Tekola, Lue

2011-06-01

In-situ air sparging has evolved as an innovative technique for soil and groundwater remediation impacted with volatile organic compounds (VOCs), including chlorinated solvents. These may exist as non-aqueous phase liquid (NAPL) or dissolved in groundwater. This study assessed: (1) how air injection rate affects the mass removal of dissolved phase contamination, (2) the effect of induced groundwater flow on mass removal and air distribution during air injection, and (3) the effect of initial contaminant concentration on mass removal. Dissolved-phase chlorinated solvents can be effectively removed through the use of air sparging; however, rapid initial rates of contaminant removal are followed by a protracted period of lower removal rates, or a tailing effect. As the air flow rate increases, the rate of contaminant removal also increases, especially during the initial stages of air injection. Increased air injection rates will increase the density of air channel formation, resulting in a larger interfacial mass transfer area through which the dissolved contaminant can partition into the vapor phase. In cases of groundwater flow, increased rates of air injection lessened observed downward contaminant migration effect. The air channel network and increased air saturation reduced relative hydraulic conductivity, resulting in reduced groundwater flow and subsequent downgradient contaminant migration. Finally, when a higher initial TCE concentration was present, a slightly higher mass removal rate was observed due to higher volatilization-induced concentration gradients and subsequent diffusive flux. Once concentrations are reduced, a similar tailing effect occurs.

Alcohol based-deep eutectic solvent (DES) as an alternative green additive to increase rotenone yield

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

Othman, Zetty Shafiqa; Hassan, Nur Hasyareeda; Zubairi, Saiful Irwan

Deep eutectic solvents (DESs) are basically molten salts that interact by forming hydrogen bonds between two added components at a ratio where eutectic point reaches a melting point lower than that of each individual component. Their remarkable physicochemical properties (similar to ionic liquids) with remarkable green properties, low cost and easy handling make them a growing interest in many fields of research. Therefore, the objective of pursuing this study is to analyze the potential of alcohol-based DES as an extraction medium for rotenone extraction from Derris elliptica roots. DES was prepared by a combination of choline chloride, ChCl and 1,more » 4-butanediol at a ratio of 1/5. The structure of elucidation of DES was analyzed using FTIR, {sup 1}H-NMR and {sup 13}C-NMR. Normal soaking extraction (NSE) method was carried out for 14 hours using seven different types of solvent systems of (1) acetone; (2) methanol; (3) acetonitrile; (4) DES; (5) DES + methanol; (6) DES + acetonitrile; and (7) [BMIM] OTf + acetone. Next, the yield of rotenone, % (w/w), and its concentration (mg/ml) in dried roots were quantitatively determined by means of RP-HPLC. The results showed that a binary solvent system of [BMIM] OTf + acetone and DES + acetonitrile was the best solvent system combination as compared to other solvent systems. It contributed to the highest rotenone content of 0.84 ± 0.05% (w/w) (1.09 ± 0.06 mg/ml) and 0.84 ± 0.02% (w/w) (1.03 ± 0.01 mg/ml) after 14 hours of exhaustive extraction time. In conclusion, a combination of the DES with a selective organic solvent has been proven to have a similar potential and efficiency as of ILs in extracting bioactive constituents in the phytochemical extraction process.« less

Interaction between morin and AOT reversed micelles--studies with UV-vis at 25 °C.

PubMed

Bhattarai, Ajaya; Wilczura-Wachnik, H

2014-01-30

The precise measurements of morin absorbance in presence of surfactant/solvent/water systems at 25 °C by UV-vis technique are reported. The surfactant used in presented study was sodium bis(2-ethylhexyl) sulfosuccinate called Aerosol-OT or AOT. The solvents selected were: ethanol, ethylene glycol, and n-decanol. The concentrations of AOT were varied between 0.001 and 0.4 mol/kg. Morin concentration in quvette during UV-vis registration was not equals in all solvent because of its different solubility and absorption intensity depending on the solvent. Water concentration in the studied systems was defined by R parameter according to relation: R=[H2O]/[AOT] and was equal 0, 30 and 40 in ethanol; 0, 10, 20 and 30 in ethylene glycol and 0, 10, 20, 30, and 40 in n-decanol. In presented work a Nernstian distribution of morin between the organic and micellar phases was assumed. The intensity of morin absorbance as a function of AOT concentration was analyzed. Using Non-linear Regression Procedure (NLREG) morin binding constant (K' [mol/kg]), and morin distribution constant (K) between organic phase and AOT micellar phase have been calculated. The experimental results have shown a significant influence of solvent, surfactant and water presence on morin UV-vis spectrum. Calculated data pointed out on different transfer of morin molecules from the organic to micellar phase depending on the solvent. Moreover, results of calculations indicate on competition between morin and water molecules interacting with AOT polar heads. Morin molecules privileged location in AOT reversed micelles strongly depends on the solvent. In case of systems with ethylene glycol as solvent is possible morin molecules location in polar cores of AOT reversed micelles as results of strong interaction between AOT polar heads and morin hydroxyl groups, whereas in case of ethanol and n-decanol morin molecules are located in palisade layer. Copyright © 2013 Elsevier B.V. All rights reserved.

Control of morphology and function of low band gap polymer–bis-fullerene mixed heterojunctions in organic photovoltaics with selective solvent vapor annealing

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

Chen, Huipeng; Hsiao, Yu-Che; Hu, Bin

2014-05-07

We reported how by replacing PCBM with a bis-adduct fullerene (i.e. ICBA) we significantly improve the open circuit voltage (VOC) and power conversion efficiency (PCE) in P3HT bulk heterojunctions. But, for the most promising low band-gap polymer (LBP) systems, replacing PCBM with ICBA results in very poor shortcircuit current (JSC) and PCE although the VOC is significantly improved. Therefore, in this work, we have completed small angle neutron scattering and neutron reflectometry experiments to study the impact of post-deposition solvent annealing (SA) with control of solvent quality on the morphology and performance of LBP bis-fullerene BHJ photovoltaics. Our results showmore » that SA in a solvent that is selective for the LBP results in a depletion of bis-fullerene near the air surface, which limits device performance. SA in a solvent vapor which has similar solubility for polymer and bis-fullerene results in a higher degree of polymer ordering, bis-fullerene phase separation, and segregation of the bis-fullerene to the air surface, which facilitates charge transport and increases power conversion efficiency (PCE) by 100%. The highest degree of polymer ordering combined with significant bis-fullerene phase separation and segregation of bis-fullerene to the air surface is obtained by SA in a solvent vapor that is selective for the bis-fullerene. The resultant morphology increases PCE by 190%. These results indicate that solvent annealing with judicious solvent choice provides a unique tool to tune the morphology of LBP bisfullerene BHJ system, providing sufficient polymer ordering, formation of a bis-fullerene pure phase, and segregation of bis-fullerene to the air surface to optimize the morphology of the active layer. Furthermore, this process is broadly applicable to improving current disappointing LBP bis-fullerene systems to optimize their morphology and OPV performance post-deposition, including higher VOC and power conversion efficiency.« less

Pilot Field Test of Electrokinetically-Delivered and Thermally Activated Persulfate (EKTAP) for Remediation of Chlorinated Solvents in Clay

NASA Astrophysics Data System (ADS)

O'Carrol, D. M.; Head, N.; Chowdhury, A. I.; Inglis, A.; Garcia, A. N.; Reynolds, D. A.; Hayman, J.; Hogberg, D.; Austrins, L. M.; Sidebottom, A.; Auger, M.; Eimers, J.; Gerhard, J.

2017-12-01

Remediation of low-permeability soils that are contaminated with chlorinated solvents is challenging. In-situ chemical oxidation (ISCO) with persulfate is promising, however, the delivery of the oxidant by hydraulic gradient is limited in low-permeability soils. Electrokinetic (EK) enhanced transport of amendments has shown the potential to overcome these limitations. In particular, the combined technology of EK-delivered and thermally activated persulfate (EKTAP) has been recently demonstrated in the laboratory as promising in these challenging environments (Chowdhury A. I. (2016) Hydraulic and Electrokinetic Delivery of Remediants for In-situ Remediation. Electronic Thesis and Dissertation Repository, Paper 4135). This study presents the first pilot field test to evaluate EKTAP to enhance the distribution and effectiveness of persulfate in clayey soil. The pilot field test was conducted at a contaminated site formerly occupied by a chlorinated solvent production facility. In the EK transport phase, 925 L of 40 g/L persulfate was injected over 57 days, during which 9A of direct current (DC) was applied between two electrodes spaced 3 m apart. In the subsequent heating phase, 10A of alternate current (AC) was applied across the same electrodes for an additional 70 days. Extensive sampling of soil and groundwater in this EKTAP cell were compared to those from two parallel control cells, one with EK only and one with no electrodes. Results indicated that EK can significantly increase transport rates of persulfate in clayey soil. Persulfate activation primarily occurred in the period of DC application, indicating that the natural reduction capacity of the clay soil had a significant impact on persulfate decomposition. Temperature mapping indicated that AC current was able to increase soil temperatures, validating the EKTAP concept. Degradation of chlorinated compounds, in particular, 1-2, dichloroethane (1,2- DCA), was observed to be substantial in areas of persulfate delivery. Studies are ongoing to evaluate the mineral oxidation of the persulfate and how to optimize the system for both EK and ERH applications. This study nevertheless demonstrates for the first time at the field scale that EKTAP can result in enhanced amendment transport and remediation of low permeability strata.

Evaluation of Phytoremediation for Management of Chlorinated Solvents in Soil and Groundwater

EPA Pesticide Factsheets

This document is intended to aid regulators, site owners, consultants, neighbors, and other stakeholders in understanding the proper application of planted systems to remediate groundwater contaminated with halogenated solvents.

Method developments approaches in supercritical fluid chromatography applied to the analysis of cosmetics.

PubMed

Lesellier, E; Mith, D; Dubrulle, I

2015-12-04

Analyses of complex samples of cosmetics, such as creams or lotions, are generally achieved by HPLC. These analyses are often multistep gradients, due to the presence of compounds with a large range of polarity. For instance, the bioactive compounds may be polar, while the matrix contains lipid components that are rather non-polar, thus cosmetic formulations are usually oil-water emulsions. Supercritical fluid chromatography (SFC) uses mobile phases composed of carbon dioxide and organic co-solvents, allowing for good solubility of both the active compounds and the matrix excipients. Moreover, the classical and well-known properties of these mobile phases yield fast analyses and ensure rapid method development. However, due to the large number of stationary phases available for SFC and to the varied additional parameters acting both on retention and separation factors (co-solvent nature and percentage, temperature, backpressure, flow rate, column dimensions and particle size), a simplified approach can be followed to ensure a fast method development. First, suited stationary phases should be carefully selected for an initial screening, and then the other operating parameters can be limited to the co-solvent nature and percentage, maintaining the oven temperature and back-pressure constant. To describe simple method development guidelines in SFC, three sample applications are discussed in this paper: UV-filters (sunscreens) in sunscreen cream, glyceryl caprylate in eye liner and caffeine in eye serum. Firstly, five stationary phases (ACQUITY UPC(2)) are screened with isocratic elution conditions (10% methanol in carbon dioxide). Complementary of the stationary phases is assessed based on our spider diagram classification which compares a large number of stationary phases based on five molecular interactions. Secondly, the one or two best stationary phases are retained for further optimization of mobile phase composition, with isocratic elution conditions or, when necessary, two-step gradient elution. The developed methods were then applied to real cosmetic samples to assess the method specificity, with regards to matrix interferences, and calibration curves were plotted to evaluate quantification. Besides, depending on the matrix and on the studied compounds, the importance of the detector type, UV or ELSD (evaporative light-scattering detection), and of the particle size of the stationary phase is discussed. Copyright © 2015 Elsevier B.V. All rights reserved.

Characterization and tailoring of porous sol-gel dielectrics for interlayer dielectric applications

NASA Astrophysics Data System (ADS)

Rogojevic, Svetlana

A new, better insulator is needed to replace SiO2 in the next generation of microelectronic devices. The dielectric constant of porous materials can be tailored by adjusting the porosity, so that their use can be extended to more than one generation of devices. Silica xerogel films with wide range of porosities (25 90%) are fabricated by varying the rate of solvent evaporation during spin-coating. Even better porosity control is achieved by using mixtures of high and low boiling point solvents, and allowing one solvent to evaporate completely during spin-coating. The quartz crystal microbalance method was employed to measure the traces of moisture adsorbed in xerogel films of varying porosities. By employing two different surface modifiers, it is demonstrated that the level of hydrophobicity is a function of surface chemistry, and can be tailored by using a suitable surface modifier. To investigate the interaction of xerogels with other materials, metallic layers were deposited on xerogel films, and subsequently annealed. When annealed in the ambient with trace amount of oxygen, Ta and Cu films undergo morphological instabilities. These morphological changes may lead to the erroneous interpretation of the Rutherford backscattering spectra as metal diffusion. When the samples are capped with a Si3N4 layer, Cu and Ta do not show diffusion through xerogel when annealed up to 650°C. Bias-temperature stressing was conducted in order to assess Cu drift through xerogel in the presence of an electric field. Contrary to what is normally observed with other dielectrics, the leakage current and C-V curve shifts were larger with an Al electrode than with a Cu electrode. This indicates that the surface modification of xerogel can contribute to the smaller charge injection from the Cu/xerogel interface, or to the inhibition of Cu diffusion, thus offering a possibility of designing future monolayer diffusion barriers for porous materials. Two possible paths of mass transfer in porous solids are identified: bulk and surface diffusion. Three driving forces are also analyzed: concentration gradient, electric field, and curvature gradient. The model of diffusion through porous solids shows the effects of the electric field, the solid network thickness, porosity, surface and bulk diffusivity. The model is a useful tool for designing and interpreting the experiments, in order to assess the role of surface diffusion in porous materials.

Purification of semiconducting single-walled carbon nanotubes by spiral counter-current chromatography.

PubMed

Knight, Martha; Lazo-Portugal, Rodrigo; Ahn, Saeyoung Nate; Stefansson, Steingrimur

2017-02-03

Over the last decade man-made carbon nanostructures have shown great promise in electronic applications, but they are produced as very heterogeneous mixtures with different properties so the achievement of a significant commercial application has been elusive. The dimensions of single-wall carbon nanotubes are generally a nanometer wide, up to hundreds of microns long and the carbon nanotubes have anisotropic structures. They are processed to have shorter lengths but they need to be sorted by diameter and chirality. Thus counter-current chromatography methods developed for large molecules are applied to separate these compounds. A modified mixer-settler spiral CCC rotor made with 3 D printed disks was used with a polyethylene glycol-dextran 2-phase solvent system and a surfactant gradient to purify the major species in a commercial preparation. We isolated the semi-conducting single walled carbon nanotube chiral species identified by UV spectral analysis. The further development of spiral counter-current chromatography instrumentation and methods will enable the scalable purification of carbon nanotubes useful for the next generation electronics. Copyright © 2016 Elsevier B.V. All rights reserved.

[Determination of β-sitosterol and total sterols content and antioxidant activity of oil in acai (Euterpe oleracea)].

PubMed

He, Cheng; Li, Wei; Zhang, Jian-Jun; Qu, Sheng-Sheng; Li, Jia-Jing; Wang, Lin-Yuan

2014-12-01

In order to establish a method for the determination of the sterols of the oil in the freeze-dried acai (Euterpe oleracea Mart.) and to evaluate its antioxidant activities, a saponification/extraction procedure and high performance liquid chromatography (HPLC) analysis method were developed and validated for the analysis of phytosterols in PEE (Petroleum ether extract). Separation was achieved on a Purosper STAR LP C18 column with a binary, gradient solvent system of acetonitrile and isopropanol. Evaporative light scattering detection (ELSD) was used to quantify β-sitosterol and the total sterols. Peak identification was verified by retention times and spikes with external standards. Standard curves were constructed (r = 0.999 2) to allow for sample quantification. Recovery of the saponification and extraction was demonstrated via analysis of spiked samples. The highest content of total sterols is β-sitosterol. The antioxidant activities of the extracts were evaluated using the total oxyradical scavenging capacity assay (TOSC assay). The result showed that the PEE exhibited significant antioxidant properties, sample concentration and the antioxidant capacity had a certain relevance.

Molecular Simulation Evaluation of Macromolecular Transport through Nanofiltration Membranes

NASA Astrophysics Data System (ADS)

Almodovar Arbelo, Noelia; Boudouris, Bryan; Corti, David

A hybrid Monte Carlo and Molecular Dynamics simulation technique was implemented to elucidate the equilibrium behavior and transport properties of a model macromolecule as it navigated across a nanoporous polymer thin film (i.e., a nanofiltration membrane). The model linear homopolymer chosen was one that had interactions that were representative of poly(ethylene oxide) (PEO) due to the known interactions of PEO with solution molecules when a PEO chain is dissolved in an aqueous environment. The structural rearrangements of the PEO chain as it passes through the nanopore under an imposed chemical potential gradient was quantified as a function of solvent quality, polymer chain length, nanopore diameter and shape, and PEO-nanopore wall interactions. Thus, these computational studies provide a more detailed picture of the underlying physical mechanisms that drive macromolecular transport through nanopores, and, in particular, how dimensionally-large macromolecules (i.e., with large radii of gyration) enter and move through dimensionally-small pores (i.e., small radii nanopores). The insights gained from these studies will aid in the development of more cost-effective water purification systems in separation technologies for myriad industrial applications.

Solutal Marangoni flow as the cause of ring stains from drying salty colloidal drops

NASA Astrophysics Data System (ADS)

Marin, Alvaro; Karpitschka, Stefan; Rossi, Massimiliano; Kaehler, Christian J.; Noguera-Marin, Diego; Rodriguez-Valverde, Miguel A.

2017-11-01

Salts can be found in different forms in almost any evaporating droplet in nature, our homes and in laboratories. The transport processes in such apparently simple systems differ strongly from `sweet' evaporating droplets since the liquid flows in the inverse direction due to Marangoni stresses at the surface. Such an effect has crucial consequences to salt crystallization processes and to the evaporation itself. In this work we show measurements that not only confirm clearly the details of the inverted flow patterns, but also permit us to calculate the surface tension gradients responsible for the reversal. Such a reversal does not prevent the coffee-stain effect; on the contrary, particles accumulate and get trapped at the liquid-air interface driven by the surface flow. In order to prove this, we show measurements of the full three-dimensional flow inside the evaporating salty droplet, confocal imaging is used to quantify the growth of the particle deposits for different salt concentrations, and we compare the experimental results with numerical simulations that capture the solvent evaporation, the evaporation-induced liquid flow and the quasi-equilibrium liquid-gas interface.

The early indicators of financial failure: a study of bankrupt and solvent health systems.

PubMed

Coyne, Joseph S; Singh, Sher G

2008-01-01

This article presents a series of pertinent predictors of financial failure based on analysis of solvent and bankrupt health systems to identify which financial measures show the clearest distinction between success and failure. Early warning signals are evident from the longitudinal analysis as early as five years before bankruptcy. The data source includes seven years of annual statements filed with the Securities and Exchange Commission by 13 health systems before they filed bankruptcy. Comparative data were compiled from five solvent health systems for the same seven-year period. Seven financial solvency ratios are included in this study, including four cash liquidity measures, two leverage measures, and one efficiency measure. The results show distinct financial trends between solvent and bankrupt health systems, in particular for the operating-cash-flow-related measures, namely Ratio 1: Operating Cash Flow Percentage Change, from prior to current period; Ratio 2: Operating Cash Flow to Net Revenues; and Ratio 4: Cash Flow to Total Liabilities, indicating sensitivity in the hospital industry to cash flow management. The high dependence on credit from third-party payers is cited as a reason for this; thus, there is a great need for cash to fund operations. Five managerial policy implications are provided to help health system managers avoid financial solvency problems in the future.

Nonflammable, Nonaqueous, Low Atmospheric Impact, High Performance Cleaning Solvents

NASA Technical Reports Server (NTRS)

Dhooge, P. M.; Glass, S. M.; Nimitz, J. S.

2001-01-01

For many years, chlorofluorocarbon (CFC) and chlorocarbon solvents have played an important part in aerospace operations. These solvents found extensive use as cleaning and analysis (EPA) solvents in precision and critical cleaning. However, CFCs and chlorocarbon solvents have deleterious effects on the ozone layer, are relatively strong greenhouse gases, and some are suspect or known carcinogens. Because of their ozone-depletion potential (ODP), the Montreal Protocol and its amendments, as well as other environmental regulations, have resulted in the phaseout of CFC-113 and 1,1,1-trichloroethane (TCA). Although alternatives have been recommended, they do not perform as well as the original solvents. In addition, some analyses, such as the infrared analysis of extracted hydrocarbons, cannot be performed with the substitute solvents that contain C-H bonds. CFC-113 solvent has been used for many critical aerospace applications. CFC-113, also known as Freon (registered) TF, has been used extensively in NASA's cleaning facilities for precision and critical cleaning, in particular the final rinsing in Class 100 areas, with gas chromatography analysis of rinse residue. While some cleaning can be accomplished by other processes, there are certain critical applications where CFC-113 or a similar solvent is highly cost-effective and ensures safety. Oxygen system components are one example where a solvent compatible with oxygen and capable of removing fluorocarbon grease is needed. Electronic components and precision mechanical components can also be damaged by aggressive cleaning solvents.

Water dynamics in small reverse micelles in two solvents: two-dimensional infrared vibrational echoes with two-dimensional background subtraction.

PubMed

Fenn, Emily E; Wong, Daryl B; Fayer, M D

2011-02-07

Water dynamics as reflected by the spectral diffusion of the water hydroxyl stretch were measured in w(0) = 2 (1.7 nm diameter) Aerosol-OT (AOT)/water reverse micelles in carbon tetrachloride and in isooctane solvents using ultrafast 2D IR vibrational echo spectroscopy. Orientational relaxation and population relaxation are observed for w(0) = 2, 4, and 7.5 in both solvents using IR pump-probe measurements. It is found that the pump-probe observables are sensitive to w(0), but not to the solvent. However, initial analysis of the vibrational echo data from the water nanopool in the reverse micelles in the isooctane solvent seems to yield different dynamics than the CCl(4) system in spite of the fact that the spectra, vibrational lifetimes, and orientational relaxation are the same in the two systems. It is found that there are beat patterns in the interferograms with isooctane as the solvent. The beats are observed from a signal generated by the AOT/isooctane system even when there is no water in the system. A beat subtraction data processing procedure does a reasonable job of removing the distortions in the isooctane data, showing that the reverse micelle dynamics are the same within experimental error regardless of whether isooctane or carbon tetrachloride is used as the organic phase. Two time scales are observed in the vibrational echo data, ~1 and ~10 ps. The slower component contains a significant amount of the total inhomogeneous broadening. Physical arguments indicate that there is a much slower component of spectral diffusion that is too slow to observe within the experimental window, which is limited by the OD stretch vibrational lifetime.

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

PubMed

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

2017-09-01

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

Water dynamics in small reverse micelles in two solvents: Two-dimensional infrared vibrational echoes with two-dimensional background subtraction

NASA Astrophysics Data System (ADS)

Fenn, Emily E.; Wong, Daryl B.; Fayer, M. D.

2011-02-01

Water dynamics as reflected by the spectral diffusion of the water hydroxyl stretch were measured in w0 = 2 (1.7 nm diameter) Aerosol-OT (AOT)/water reverse micelles in carbon tetrachloride and in isooctane solvents using ultrafast 2D IR vibrational echo spectroscopy. Orientational relaxation and population relaxation are observed for w0 = 2, 4, and 7.5 in both solvents using IR pump-probe measurements. It is found that the pump-probe observables are sensitive to w0, but not to the solvent. However, initial analysis of the vibrational echo data from the water nanopool in the reverse micelles in the isooctane solvent seems to yield different dynamics than the CCl4 system in spite of the fact that the spectra, vibrational lifetimes, and orientational relaxation are the same in the two systems. It is found that there are beat patterns in the interferograms with isooctane as the solvent. The beats are observed from a signal generated by the AOT/isooctane system even when there is no water in the system. A beat subtraction data processing procedure does a reasonable job of removing the distortions in the isooctane data, showing that the reverse micelle dynamics are the same within experimental error regardless of whether isooctane or carbon tetrachloride is used as the organic phase. Two time scales are observed in the vibrational echo data, ~1 and ~10 ps. The slower component contains a significant amount of the total inhomogeneous broadening. Physical arguments indicate that there is a much slower component of spectral diffusion that is too slow to observe within the experimental window, which is limited by the OD stretch vibrational lifetime.

New developments using carbon dioxide as a solvent: Monolayers and nanocomposites. 1. Reactions of organosilanes with oxidized silicon surfaces in carbon dioxide. 2. Polymer/polymer nanocomposites synthesized in carbon dioxide

NASA Astrophysics Data System (ADS)

Cao, Chuntao

The aim of this research was to explore new directions for carbon dioxide. The first project emphasized silyl monolayer synthesis. Silylation reactions were performed in both liquid and supercritical carbon dioxide. Different monofunctional organosilanes reacted with silica surfaces, forming covalently attached monolayers. These monolayers were characterized using contact angle measurements, X-ray photoelectron spectroscopy, and ellipsometry. Reaction kinetics were established, and compared with silylations in organic solvents. The reaction rate in CO2 is higher than that in conventional solvents while the final coverage is slightly lower than the optimized conditions for conventional solvents. Other multi-functional silanes were also studied. The silylation of nanoporous silica surfaces showed bonding densities almost as high as the maximum value reported in literature for small-pore substrates. Overall, CO2 is a good solvent for silylations on silica surfaces. The second project was to synthesize polymer/polymer nanocomposites using a CO2-assisted templating method. Semicrystalline polymers are composed of tens-of-nanometer thick crystalline lamellae and an amorphous matrix. CO2 normally swells only the amorphous and interlamellar regions. The goal of this research was to selectively bring monomers to the amorphous and interlamellar regions with the help of CO2. In situ polymerization and precipitation fixes the structure, replicating the nano-structure of the semicrystalline polymer substrate. Ring-opening metathesis polymerization was performed inside of CO2-swollen poly(4-methyl-1-pentene) (PMP) of high crystallinity. Several polymer/polymer nanocomposites were successfully produced using this method. They were characterized by a variety of techniques, such as transmission electron microscopy (TEM), differential scanning calorimetry (DSC), thermal gravimetric analysis (TGA) and wide angle X-ray diffraction (WAXD). Infrared studies and TEM indicated that one type of composite, polynorbomene/PMP, had a gradient distribution of polynorbornene inside of the PMP matrix. Another composite, polyoctenamer/PMP prepared by cis-cyclooctene polymerization, exhibited very interesting mechanical properties. The poly(dicyclopentadiene)/PMP composites are unique nanometer-scale blends of a highly crosslinked thermoset with a thermoplastic polymer.

Barium titanate tape properties for MLCC application using different binder systems

NASA Astrophysics Data System (ADS)

Yoon, Dang-Hyok

Most of multilayer ceramic capacitor (MLCC) industries are currently using solvent-based slip systems, although water-based slips have been receiving increasing attention due to reduced health and environmental hazards. The current work focuses on two main fields to meet the challenges in MLCC processing in aqueous media. One is the comparison between water- and solvent-based slip systems using design of experiments (DOE). The other is the understanding of Ba2+ ion leaching behavior in water and its effect on tape properties. For the first part, twenty four kinds of BaTiO3 slips were investigated using three different binder systems: one solvent-based, and two water-based systems. Tape casting, sintering and characterization were conducted. Slip viscosity and tape strength of the green tape depended significantly on the binder type. It was possible to achieve a higher green density for water-based system than that for a solvent-based one. Most of the green body properties from solvent-based system depended on the ceramic powder. On the other hand, the dispersant was the most significant factor for the green body properties of two water-based systems. Sintered properties such as microstructure and dielectric permittivity for three systems depended significantly on the type of ceramic powder. An optimization was performed for each system by means of a scorecard. By choosing the optimum condition, comparable results were drawn for the water-based system compared to a solvent-based one for MLCC application. For the second part, the amount of Ba2+ ion leaching from BaTiO3 in water was determined by an EDTA titration method. The greater extent and the faster rate of Ba2+ leaching were found at the lower solution pH. The excess free barium ions expressed by means of the Ba/Ti ratio adversely affected most tape properties. To passivate BaTiO 3 surface from Ba2+ ion leaching in water, passivation agent layer (PAL) was formed by drying the slurry after adding a commercial polymeric dispersant. Compared to the conventional dispersant adding method, this PAL method was more effective in reducing the amount of Ba2+ leaching. Moreover, using PAL did not deteriorate any of green and sintered properties of BaTiO3 tape.

The Interaction of Spacecraft Cabin Atmospheric Quality and Water Processing System Performance

NASA Technical Reports Server (NTRS)

Perry, Jay L.; Croomes, Scott D. (Technical Monitor)

2002-01-01

Although designed to remove organic contaminants from a variety of waste water streams, the planned U.S.- and present Russian-provided water processing systems onboard the International Space Station (ISS) have capacity limits for some of the more common volatile cleaning solvents used for housekeeping purposes. Using large quantities of volatile cleaning solvents during the ground processing and in-flight operational phases of a crewed spacecraft such as the ISS can lead to significant challenges to the water processing systems. To understand the challenges facing the management of water processing capacity, the relationship between cabin atmospheric quality and humidity condensate loading is presented. This relationship is developed as a tool to determine the cabin atmospheric loading that may compromise water processing system performance. A comparison of cabin atmospheric loading with volatile cleaning solvents from ISS, Mir, and Shuttle are presented to predict acceptable limits to maintain optimal water processing system performance.

Reach-scale characterization of large woody debris in a low-gradient, Midwestern U.S.A. river system

NASA Astrophysics Data System (ADS)

Martin, Derek J.; Pavlowsky, Robert T.; Harden, Carol P.

2016-06-01

Addition of large woody debris (LWD) to rivers has increasingly become a popular stream restoration strategy, particularly in river systems of the Midwestern United States. However, our knowledge of LWD dynamics is mostly limited to high gradient montane river systems, or coastal river systems. The LWD-related management of low-gradient, Midwestern river systems is thus largely based on higher gradient analogs of LWD dynamics. This research characterizes fluvial wood loads and investigates the relationships between fluvial wood, channel morphology, and sediment deposition in a relatively low-gradient, semiconfined, alluvial river. The LWD and channel morphology were surveyed at nine reaches along the Big River in southeastern Missouri to investigate those relationships in comparison to other regions. Wood loads in the Big River are low (3-114 m3/100 m) relative to those of higher gradient river systems of the Pacific Northwest, but high relative to lower-gradient river systems of the Eastern United States. Wood characteristics such as size and orientation suggest that the dominant LWD recruitment mechanism in the Big River is bank erosion. Also, ratios of wood geometry to channel geometry show that the Big River maintains a relatively high wood transport capacity for most of its length. Although LWD creates sites for sediment storage, the overall impact on reach-scale sediment storage in the Big River is low (< 4.2% of total in-channel storage). However, wood loads, and thus opportunities for sediment storage, have the potential to grow in the future as Midwestern riparian forests mature. This study represents the first of its kind within this particular type of river system and within this region and thus serves as a basis for understanding fluvial wood dynamics in low-gradient river systems of the Midwestern United States.

Arbitrary magnetic field gradient waveform correction using an impulse response based pre-equalization technique.

PubMed

Goora, Frédéric G; Colpitts, Bruce G; Balcom, Bruce J

2014-01-01

The time-varying magnetic fields used in magnetic resonance applications result in the induction of eddy currents on conductive structures in the vicinity of both the sample under investigation and the gradient coils. These eddy currents typically result in undesired degradations of image quality for MRI applications. Their ubiquitous nature has resulted in the development of various approaches to characterize and minimize their impact on image quality. This paper outlines a method that utilizes the magnetic field gradient waveform monitor method to directly measure the temporal evolution of the magnetic field gradient from a step-like input function and extracts the system impulse response. With the basic assumption that the gradient system is sufficiently linear and time invariant to permit system theory analysis, the impulse response is used to determine a pre-equalized (optimized) input waveform that provides a desired gradient response at the output of the system. An algorithm has been developed that calculates a pre-equalized waveform that may be accurately reproduced by the amplifier (is physically realizable) and accounts for system limitations including system bandwidth, amplifier slew rate capabilities, and noise inherent in the initial measurement. Significant improvements in magnetic field gradient waveform fidelity after pre-equalization have been realized and are summarized. Copyright © 2013 Elsevier Inc. All rights reserved.

The generation of concentration gradients using electroosmotic flow in micro reactors allowing stereoselective chemical synthesis.

PubMed

Skelton, V; Greenway, G M; Haswell, S J; Styring, P; Morgan, D O; Warrington, B H; Wong, S Y

2001-01-01

The stereoselective control of chemical reactions has been achieved by applying electrical fields in a micro reactor generating controlled concentration gradients of the reagent streams. The chemistry based upon well-established Wittig synthesis was carried out in a micro reactor device fabricated in borosilicate glass using photolithographic and wet etching techniques. The selectivity of the cis (Z) to trans (E) isomeric ratio in the product synthesised was controlled by varying the applied voltages to the reagent reservoirs within the micro reactor. This subsequently altered the relative reagent concentrations within the device resulting in Z/E ratios in the range 0.57-5.21. By comparison, a traditional batch method based on the same reaction length, concentration, solvent and stoichiometry (i.e., 1.0:1.5:1.0 reagent ratios) gave a Z/E in the range 2.8-3.0. However, when the stoichiometric ratios were varied up to ten times as much, the Z/E ratios varied in accordance to the micro reactor i.e., when the aldehyde is in excess, the Z isomer predominates whereas when the aldehyde is in low concentrations, the E isomer is the more favourable form. Thus indicating that localised concentration gradients generated by careful flow control due to the diffusion limited non-turbulent mixing regime within a micro reactor, leads to the observed stereo selectivity for the cis and trans isomers.

Trace elements retained in washed nuclear fuel reprocessing solvents

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

Gray, L.W.; MacMurdo, K.W.

1979-09-01

Analysis of purified TBP extractant from solvent extraction processes at Savannah River Plant showed several stable elements and several long-lived radioisotopes. Stable elements Al, Na, Br, Ce, Hg, and Sm are found in trace quantities in the solvent. The only stable metallic element consistently found in the solvent was Al, with a concentration which varies from about 30 ppM to about 10 ppM. The halogens Br and Cl appear to be found in the solvent systems as organo halides. Radionuclides found were principally /sup 106/Ru, /sup 129/I, /sup 3/H, /sup 235/U, and /sup 239/Pu. The /sup 129/I concentration was aboutmore » 1 ppM in the first solvent extraction cycle of each facility. In the other cycles, /sup 129/I concentration varied from about 0.1 to 0.5 ppM. Both /sup 129/I and /sup 3/H appear to be in the organic solvent as a result of exchange with hydrogen.« less

Assessing implicit models for nonpolar mean solvation forces: The importance of dispersion and volume terms

PubMed Central

Wagoner, Jason A.; Baker, Nathan A.

2006-01-01

Continuum solvation models provide appealing alternatives to explicit solvent methods because of their ability to reproduce solvation effects while alleviating the need for expensive sampling. Our previous work has demonstrated that Poisson-Boltzmann methods are capable of faithfully reproducing polar explicit solvent forces for dilute protein systems; however, the popular solvent-accessible surface area model was shown to be incapable of accurately describing nonpolar solvation forces at atomic-length scales. Therefore, alternate continuum methods are needed to reproduce nonpolar interactions at the atomic scale. In the present work, we address this issue by supplementing the solvent-accessible surface area model with additional volume and dispersion integral terms suggested by scaled particle models and Weeks–Chandler–Andersen theory, respectively. This more complete nonpolar implicit solvent model shows very good agreement with explicit solvent results and suggests that, although often overlooked, the inclusion of appropriate dispersion and volume terms are essential for an accurate implicit solvent description of atomic-scale nonpolar forces. PMID:16709675

Effect of reaction solvent on hydroxyapatite synthesis in sol-gel process

NASA Astrophysics Data System (ADS)

Nazeer, Muhammad Anwaar; Yilgor, Emel; Yagci, Mustafa Baris; Unal, Ugur; Yilgor, Iskender

2017-12-01

Synthesis of hydroxyapatite (HA) through sol-gel process in different solvent systems is reported. Calcium nitrate tetrahydrate (CNTH) and diammonium hydrogen phosphate (DAHP) were used as calcium and phosphorus precursors, respectively. Three different synthesis reactions were carried out by changing the solvent media, while keeping all other process parameters constant. A measure of 0.5 M aqueous DAHP solution was used in all reactions while CNTH was dissolved in distilled water, tetrahydrofuran (THF) and N,N-dimethylformamide (DMF) at a concentration of 0.5 M. Ammonia solution (28-30%) was used to maintain the pH of the reaction mixtures in the 10-12 range. All reactions were carried out at 40 ± 2°C for 4 h. Upon completion of the reactions, products were filtered, washed and calcined at 500°C for 2 h. It was clearly demonstrated through various techniques that the dielectric constant and polarity of the solvent mixture strongly influence the chemical structure and morphological properties of calcium phosphate synthesized. Water-based reaction medium, with highest dielectric constant, mainly produced β-calcium pyrophosphate (β-CPF) with a minor amount of HA. DMF/water system yielded HA as the major phase with a very minor amount of β-CPF. THF/water solvent system with the lowest dielectric constant resulted in the formation of pure HA.

Metabolic gradients: a new system for old questions.

PubMed

Blackstone, Neil W

2008-04-22

Metabolic gradients are likely to be crucial to normal and abnormal development of cells and tissues. As shown by a new study, a Xenopus egg model system has great promise to illuminate quantitative measures of metabolic gradients in living cytoplasm.

Connecting Free Energy Surfaces in Implicit and Explicit Solvent: an Efficient Method to Compute Conformational and Solvation Free Energies

PubMed Central

Deng, Nanjie; Zhang, Bin W.; Levy, Ronald M.

2015-01-01

The ability to accurately model solvent effects on free energy surfaces is important for understanding many biophysical processes including protein folding and misfolding, allosteric transitions and protein-ligand binding. Although all-atom simulations in explicit solvent can provide an accurate model for biomolecules in solution, explicit solvent simulations are hampered by the slow equilibration on rugged landscapes containing multiple basins separated by barriers. In many cases, implicit solvent models can be used to significantly speed up the conformational sampling; however, implicit solvent simulations do not fully capture the effects of a molecular solvent, and this can lead to loss of accuracy in the estimated free energies. Here we introduce a new approach to compute free energy changes in which the molecular details of explicit solvent simulations are retained while also taking advantage of the speed of the implicit solvent simulations. In this approach, the slow equilibration in explicit solvent, due to the long waiting times before barrier crossing, is avoided by using a thermodynamic cycle which connects the free energy basins in implicit solvent and explicit solvent using a localized decoupling scheme. We test this method by computing conformational free energy differences and solvation free energies of the model system alanine dipeptide in water. The free energy changes between basins in explicit solvent calculated using fully explicit solvent paths agree with the corresponding free energy differences obtained using the implicit/explicit thermodynamic cycle to within 0.3 kcal/mol out of ~3 kcal/mol at only ~8 % of the computational cost. We note that WHAM methods can be used to further improve the efficiency and accuracy of the explicit/implicit thermodynamic cycle. PMID:26236174

Connecting free energy surfaces in implicit and explicit solvent: an efficient method to compute conformational and solvation free energies.

PubMed

Deng, Nanjie; Zhang, Bin W; Levy, Ronald M

2015-06-09

The ability to accurately model solvent effects on free energy surfaces is important for understanding many biophysical processes including protein folding and misfolding, allosteric transitions, and protein–ligand binding. Although all-atom simulations in explicit solvent can provide an accurate model for biomolecules in solution, explicit solvent simulations are hampered by the slow equilibration on rugged landscapes containing multiple basins separated by barriers. In many cases, implicit solvent models can be used to significantly speed up the conformational sampling; however, implicit solvent simulations do not fully capture the effects of a molecular solvent, and this can lead to loss of accuracy in the estimated free energies. Here we introduce a new approach to compute free energy changes in which the molecular details of explicit solvent simulations are retained while also taking advantage of the speed of the implicit solvent simulations. In this approach, the slow equilibration in explicit solvent, due to the long waiting times before barrier crossing, is avoided by using a thermodynamic cycle which connects the free energy basins in implicit solvent and explicit solvent using a localized decoupling scheme. We test this method by computing conformational free energy differences and solvation free energies of the model system alanine dipeptide in water. The free energy changes between basins in explicit solvent calculated using fully explicit solvent paths agree with the corresponding free energy differences obtained using the implicit/explicit thermodynamic cycle to within 0.3 kcal/mol out of ∼3 kcal/mol at only ∼8% of the computational cost. We note that WHAM methods can be used to further improve the efficiency and accuracy of the implicit/explicit thermodynamic cycle.

Microfluidic platform for optimization of crystallization conditions

NASA Astrophysics Data System (ADS)

Zhang, Shuheng; Gerard, Charline J. J.; Ikni, Aziza; Ferry, Gilles; Vuillard, Laurent M.; Boutin, Jean A.; Ferte, Nathalie; Grossier, Romain; Candoni, Nadine; Veesler, Stéphane

2017-08-01

We describe a universal, high-throughput droplet-based microfluidic platform for crystallization. It is suitable for a multitude of applications, due to its flexibility, ease of use, compatibility with all solvents and low cost. The platform offers four modular functions: droplet formation, on-line characterization, incubation and observation. We use it to generate droplet arrays with a concentration gradient in continuous long tubing, without using surfactant. We control droplet properties (size, frequency and spacing) in long tubing by using hydrodynamic empirical relations. We measure droplet chemical composition using both an off-line and a real-time on-line method. Applying this platform to a complicated chemical environment, membrane proteins, we successfully handle crystallization, suggesting that the platform is likely to perform well in other circumstances. We validate the platform for fine-gradient screening and optimization of crystallization conditions. Additional on-line detection methods may well be integrated into this platform in the future, for instance, an on-line diffraction technique. We believe this method could find applications in fields such as fluid interaction engineering, live cell study and enzyme kinetics.

A validated stability-indicating UPLC method for desloratadine and its impurities in pharmaceutical dosage forms.

PubMed

Rao, Dantu Durga; Satyanarayana, N V; Malleswara Reddy, A; Sait, Shakil S; Chakole, Dinesh; Mukkanti, K

2010-02-05

A novel stability-indicating gradient reverse phase ultra-performance liquid chromatographic (RP-UPLC) method was developed for the determination of purity of desloratadine in presence of its impurities and forced degradation products. The method was developed using Waters Aquity BEH C18 column with mobile phase containing a gradient mixture of solvents A and B. The eluted compounds were monitored at 280nm. The run time was 8min within which desloratadine and its five impurities were well separated. Desloratadine was subjected to the stress conditions of oxidative, acid, base, hydrolytic, thermal and photolytic degradation. Desloratadine was found to degrade significantly in oxidative and thermal stress conditions and stable in acid, base, hydrolytic and photolytic degradation conditions. The degradation products were well resolved from main peak and its impurities, thus proved the stability-indicating power of the method. The developed method was validated as per ICH guidelines with respect to specificity, linearity, limit of detection, limit of quantification, accuracy, precision and robustness. This method was also suitable for the assay determination of desloratadine in pharmaceutical dosage forms.

On the relation between Marcus theory and ultrafast spectroscopy of solvation kinetics

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

Roy, Santanu; Galib, Mirza; Schenter, Gregory K.

The phenomena of solvent exchange control the process of solvating ions, protons, and charged molecules. Building upon our extension of Marcus’ philosophy of electron transfer, here we provide a new perspective of ultrafast solvent exchange mechanism around ions measurable by two-dimensional infrared (2DIR) spectroscopy. In this theory, solvent rearrangement drives an ion-bound water to an activated state of higher coordination number, triggering ion-water separation that leads to the solvent-bound state of the water molecule. This ion-bound to solvent-bound transition rate for a BF 4 --water system is then computed using ab initio molecular dynamics and Marcus theory, and is foundmore » to be in excellent agreement with the 2DIR measurement.« less

On the relation between Marcus theory and ultrafast spectroscopy of solvation kinetics

DOE PAGES

Roy, Santanu; Galib, Mirza; Schenter, Gregory K.; ...

2017-12-24

The phenomena of solvent exchange control the process of solvating ions, protons, and charged molecules. Building upon our extension of Marcus’ philosophy of electron transfer, here we provide a new perspective of ultrafast solvent exchange mechanism around ions measurable by two-dimensional infrared (2DIR) spectroscopy. In this theory, solvent rearrangement drives an ion-bound water to an activated state of higher coordination number, triggering ion-water separation that leads to the solvent-bound state of the water molecule. This ion-bound to solvent-bound transition rate for a BF 4 --water system is then computed using ab initio molecular dynamics and Marcus theory, and is foundmore » to be in excellent agreement with the 2DIR measurement.« less

On the relation between Marcus theory and ultrafast spectroscopy of solvation kinetics

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

Roy, Santanu; Galib, Mirza; Schenter, Gregory K.

The phenomena of solvent exchange control the process of solvating ions, protons, and charged molecules. Building upon our extension of Marcus’ philosophy of electron transfer, we provide a new perspective of ultrafast solvent exchange mechanism around ions measurable by two-dimensional infrared (2DIR) spectroscopy. In this theory, solvent rearrangement drives an ion-bound water to an activated state of higher coordination number, triggering ion-water separation that leads to the solvent-bound state of the water molecule. This ion-bound to solvent-bound transition rate for a BF4- water system is computed using ab initio molecular dynamics and Marcus theory, and is found to be inmore » excellent agreement with the 2DIR measurement.« less

Solvent Dependence of Lateral Charge Transfer in a Porphyrin Monolayer

DOE PAGES

Brennan, Bradley J.; Regan, Kevin P.; Durrell, Alec C.; ...

2016-12-19

Lateral charge transport in a redox)active monolayer can be utilized for solar energy harvesting. We chose the porphyrin system to study the influence of the solvent on lateral hole hopping, which plays a crucial role in the charge)transfer kinetics. We also examined the influence of water, acetonitrile, and propylene carbonate as solvents. Hole)hopping lifetimes varied by nearly three orders of magnitude among solvents, ranging from 3 ns in water to 2800 ns in propylene carbonate, and increased nonlinearly as a function of added acetonitrile in aqueous solvent mixtures. Our results elucidate the important roles of solvation, molecular packing dynamics, andmore » lateral charge)transfer mechanisms that have implications for all dye)sensitized photoelectrochemical device designs.« less

Changing the Mechanism for CO 2 Hydrogenation Using Solvent-Dependent Thermodynamics

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

Burgess, Samantha A.; Appel, Aaron M.; Linehan, John C.

A critical scientific challenge for utilization of CO2 is the development of catalyst systems that do not depend upon expensive or environmentally unfriendly reagents, such as precious metals, strong organic bases, and organic solvents. We have used thermodynamic insights to predict and demonstrate that the HCoI(dmpe)2 catalyst system, previously described for use in organic solvents, can hydrogenate CO2 to formate in water with bicarbonate as the only added reagent. Replacing tetrahydrofuran as the solvent with water changes the mechanism for catalysis by altering the thermodynamics for hydride transfer to CO2 from a key dihydride intermediate. The need for a strongmore » organic base was eliminated by performing catalysis in water due to the change in mechanism. These studies demonstrate that the solvent plays a pivotal role in determining the reaction thermodynamics and thereby catalytic mechanism and activity. The research was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences. Pacific Northwest National Laboratory is operated by Battelle for the U.S. Department of Energy.« less

Exploring the role of ionic liquids to tune the polymorphic outcome of organic compounds.

PubMed

Zeng, Qingying; Mukherjee, Arijit; Müller, Peter; Rogers, Robin D; Myerson, Allan S

2018-02-14

While molecular solvents are commonly used in the screening of polymorphs, the choices are often restricted. Ionic liquids (ILs) - also referred as designer solvents - have immense possibility in this regard because of their wide flexibility of tunability. More importantly, the interactions among the IL components are completely unique compared to those present in the molecular solvents. In this context, we have chosen tetrolic acid (TA) and isonicotinamide (INA), which showed solution-structure link in molecular solvents in the past, as probes to investigate the role of imidazolium based ionic liquids in the polymorphism of these two systems and whether the different solute-solvent interactions in ILs affect the polymorphic outcome. It is observed that the selected imidazolium-based ILs, with varying anion basicity have influenced the crystallization outcome by the interaction between ILs and model compounds. Later, we have utilized the concept of double salt ionic liquids (DSIL) for INA, a penta-morphic system, to investigate the variation in the polymorphic outcome. This approach helped to obtain the forms that were otherwise inaccessible in ILs.

Structure of block copolymer micelles in the presence of co-solvents

NASA Astrophysics Data System (ADS)

Robertson, Megan; Wang, Shu; Le, Kim Mai; Piemonte, Rachele; Madsen, Louis

2015-03-01

Amphiphilic block copolymer micelles in water are under broad exploration for drug delivery applications due to their high loading capacity and targeted drug delivery. We aim to understand the kinetic and thermodynamic processes that underlie the self-assembly of diblock copolymer micelle systems. The present work focuses on diblock copolymers containing poly(ethylene oxide) (a hydrophilic polymer) and polycaprolactone (a hydrophobic polymer), which spontaneously self-assemble into spherical micelles in water. Addition of a common good solvent (a co-solvent) for both of the constituting blocks, such as tetrahydrofuran (THF), reduces the interfacial tension at the core-corona interface. We are currently investigating the effect of this phenomenon on the micelle structural properties, using scattering experiments and nuclear magnetic resonance. We have characterized the hydrodynamic radius, core radius, corona thickness, aggregation number, degree of swelling of the micelle core with the co-solvent, and unimer (free chain) concentration, as a function of the co-solvent concentration. Fundamental knowledge from these studies will inform design of drug delivery systems by allowing us to tailor micelle properties for optimal cargo loading.

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

NASA Astrophysics Data System (ADS)

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

2017-04-01

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

Alternative Solvents and Technologies for Precision Cleaning of Aerospace Components

NASA Technical Reports Server (NTRS)

Grandelli, Heather; Maloney, Phillip; DeVor, Robert; Hintze, Paul

2014-01-01

Precision cleaning solvents for aerospace components and oxygen fuel systems, including currently used Vertrel-MCA, have a negative environmental legacy, high global warming potential, and have polluted cleaning sites. Thus, alternative solvents and technologies are being investigated with the aim of achieving precision contamination levels of less than 1 mg/sq ft. The technologies being evaluated are ultrasonic bath cleaning, plasma cleaning and supercritical carbon dioxide cleaning.

Capping the calix: How toluene completes cesium(i) coordination with calix[4]pyrrole

DOE PAGES

Ellis, Ross J.; Reinhart, Benjamin; Williams, Neil J.; ...

2017-05-04

The role of solvent in molecular recognition systems is under-researched and often ignored, especially when the solvent is considered “non-interacting”. This study concerns the role of toluene solvent in cesium(I) recognition by calix[4]pyrrole. We show that π-donor interactions bind toluene molecules onto the open face of the cation-receptor complex, thus “capping the calix.” As a result, by characterizing this unusual aromatically-saturated complex, we show how “non-interacting” aromatic solvents can directly coordinate receptor-bound cations and thus influence recognition.

Capping the calix: How toluene completes cesium(i) coordination with calix[4]pyrrole

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

Ellis, Ross J.; Reinhart, Benjamin; Williams, Neil J.

The role of solvent in molecular recognition systems is under-researched and often ignored, especially when the solvent is considered “non-interacting”. This study concerns the role of toluene solvent in cesium(I) recognition by calix[4]pyrrole. We show that π-donor interactions bind toluene molecules onto the open face of the cation-receptor complex, thus “capping the calix.” As a result, by characterizing this unusual aromatically-saturated complex, we show how “non-interacting” aromatic solvents can directly coordinate receptor-bound cations and thus influence recognition.

Acetone-based cellulose solvent.

PubMed

Kostag, Marc; Liebert, Tim; Heinze, Thomas

2014-08-01

Acetone containing tetraalkylammonium chloride is found to be an efficient solvent for cellulose. The addition of an amount of 10 mol% (based on acetone) of well-soluble salt triethyloctylammonium chloride (Et3 OctN Cl) adjusts the solvent's properties (increases the polarity) to promote cellulose dissolution. Cellulose solutions in acetone/Et3 OctN Cl have the lowest viscosity reported for comparable aprotic solutions making it a promising system for shaping processes and homogeneous chemical modification of the biopolymer. Recovery of the polymer and recycling of the solvent components can be easily achieved. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Precision Cleaning of Oxygen Systems and Components

NASA Technical Reports Server (NTRS)

McLaughlin, Russell

2009-01-01

Currently, NASA uses Dichloropentafluoropropane (HCFC-225), a Class II ozone depleting substance (ODs), to clean contaminated oxygen systems. Starting in 20 15, the Montreal Protocols and Clean Air Act prohibit the production and importation of all hydrochlorofluorocarbons (HCFC), except for limited use in refrigeration applications. Thus, a new non-ozone depleting solvent needs to be developed for use in cleaning. Optimally, such a solvent should also be environmentally benign or green to avoid needing to replace the new solvent with yet another solvent in the future due to other environmental concerns. Work for the first year consisted of two parts. The first part was developing a method of testing the cleaning efficiency of potential solvents. Stainless steel coupons were contaminated with a known weight of various contaminants and contaminant combinations and then immersed in solvent for ten minutes. The coupons were then removed and dried in an oven until all solvent had evaporated. Once dry, the coupons were weighed and the mass of the non-volatile residue (NVR) left on the coupon was determined. The cleaning efficiency of the solvents is reported as percent cleaning, with 100% cleaning being zero NVR left on the test coupon. The second half of the first goal was to use the develop method to perform baseline testing on current solvents. The second part of the work was to begin exploring alternative cleaning solvents. A variety of hydrofluorocarbons (HFCs) were tested. Preliminary testing was also performed with ionic liquids and aqueous surfactant solutions. Once potential solvents were identified, an analysis of the performance and environmental characteristics of each was to be conducted. Four contaminants were specified for use in testing. These are Mil-Spec-H-5606 (5606), a hydraulic fluid, Mil-H-83282B (83282), another hydraulic fluid, diethylhexyl sebacate (Sebacate), and WD-40. The structures of these contaminants are all similar, with long aliphatic hydrocarbon chains of lengths between fifteen and fifty. Contaminants were tested both individually and in combination. All combinations were done with equal weights of the constituent contaminants.

Integrating ecosystem sampling, gradient modeling, remote sensing, and ecosystem simulation to create spatially explicit landscape inventories

Treesearch

Robert E. Keane; Matthew G. Rollins; Cecilia H. McNicoll; Russell A. Parsons

2002-01-01

Presented is a prototype of the Landscape Ecosystem Inventory System (LEIS), a system for creating maps of important landscape characteristics for natural resource planning. This system uses gradient-based field inventories coupled with gradient modeling remote sensing, ecosystem simulation, and statistical analyses to derive spatial data layers required for ecosystem...

Analytical validation applied to simultaneous determination of solvents dichloromethane (DCM), methyl isobutyl ketone (MIBK), tetrahydrofuran (THF) and toluene (TOL) in urine by headspace extraction and injection on chromatographic system with a flame ionization detector

NASA Astrophysics Data System (ADS)

Muna, E. D. M.; Pereira, R. P.

2016-07-01

The determination of the volatile organic solvents dichloromethane (DCM), methyl isobutyl ketone (MIBK), tetrahydrofuran (THF) and toluene (TOL) is applied on toxicological monitoring of employees in various industrial activities. The gas chromatography technique with flame ionization detector and headspace injection system has been applied. The analytical procedure developed allows the simultaneous determination of the above-mentioned solvents and the accuracy of the method was tested following the INMETRO guidelines through the DOQ-CGRE 008 Rev.04-July/2011.

Simultaneous determination of phenolic acids and flavonoids in Chenopodium formosanum Koidz. (djulis) by HPLC-DAD-ESI-MS/MS.

PubMed

Hsu, B Y; Lin, S W; Inbaraj, B Stephen; Chen, B H

2017-01-05

A high performance liquid chromatography-diode array detection-tandem mass spectrometry method (HPLC-DAD-MS/MS) was developed for simultaneous determination of phenolic acids and flavonoids in djulis (Chenopodium formosanum Koidz.), a traditional Chinese herb reported to possess vital biological activities. A high yield of phenolic acids and flavonoids was attained by employing 50% ethanol in water as the extraction solvent and shaking in a 60°C water bath for 3h. A total of 8 phenolic acids and 14 flavonoids were separated and identified within 55min by using a Poroshell 120 EC-C18 column with detection at 280nm, flow rate at 0.8mL/min, column temperature at 35°C, and a gradient solvent system of 0.1% formic acid in water and acetonitrile. Two internal standards caffeic acid and kaempferol-3-O-rutinoside were used for quantitation of phenolic acids and flavonoids in djulis respectively. The amounts of phenolic acids ranged from 11.5±0.8μg/g (caffeoyl-putrescine-derivative (2)) to 1855.3±16.9μg/g (hydroxylphenylacetic acid pentoside), while the flavonoids ranged from 19.93±2.29μg/g (quercetin-3-O-(coumaryl)-rutinoside-pentoside (1)) to 257.3±2.05μg/g (rutin-O-pentoside (2)). A high recovery (89.68-97.20%) and high reproducibility was obtained for both phenolic acids and flavonoids with the relative standard deviation (RSD) for the latter ranging from 0.09-8.22% (intra-day variability) and 0.80-8.48% (inter-day variability). This method may be applied to determination of both phenolic acids and flavonoids in food products and Chinese herbs. Copyright © 2016 Elsevier B.V. All rights reserved.

Online liquid chromatography-tandem mass spectrometry cyanide determination in blood.

PubMed

Lacroix, C; Saussereau, E; Boulanger, F; Goullé, J P

2011-04-01

An original liquid chromatography-tandem mass spectrometry (LC-MS-MS) method coupled to online extraction has been developed for cyanide determination in blood. A method involving fluorimetric detection after naphthalene-2,3-dicarboxyaldehyde (NDA) complexation by taurine in the presence of cyanide was previously described. Its performance was limited because of the absence of an internal standard (IS). Using cyanide isotope (13)C(15)N as IS allowed quantification in MS-MS. After the addition of (13)C(15)N, 25 μL of blood were diluted in water and deproteinized with methanol. Following derivatization with NDA and taurine for 10 min at 4°C, 100 μL was injected into the online LC-MS-MS system. An Oasis HLB was used as an extraction column, and a C18 Atlantis was the analytical column. The chromatographic cycle was performed with an ammonium formate (20 mM, pH 2.8) (solvent A) and acetonitrile/solvent A (90:10, v/v) gradient in 6 min. Detection was performed in negative electrospray ionization mode (ESI(-)) with a Quattro Micro. For quantification, transitions of derivatives formed with CN and (13)C(15)N were monitored, respectively, as follows: 299.3/191.3 and 301.3/193.3. The procedure was fully validated, linear from 26 to 2600 ng/mL with limit of detection of 10 ng/mL. This method, using a small blood sample, is not only simple, but also time saving. The specificity and sensitivity of LC-MS-MS coupled to online extraction and using (13)C(15)N as the IS make this method very suitable for cyanide determination in blood and could be useful in forensic toxicology.

A novel reverse phase high-performance liquid chromatography method for standardization of Orthosiphon stamineus leaf extracts.

PubMed

Saidan, Noor Hafizoh; Aisha, Abdalrahim F A; Hamil, Mohd Shahrul Ridzuan; Majid, Amin Malik Shah Abdul; Ismail, Zhari

2015-01-01

Orthosiphon stamineus Benth. (Lamiaceae) is a traditional medicinal plant which has been used in treating various ailments such as kidney diseases, bladder inflammation, arthritis and diabetes. The leaves contain high concentration of phenolic compounds, thus, rosmarinic acid (RA), 3'-hydroxy-5, 6, 7, 4'-tetramethoxyflavone (TMF), sinensetin (SIN) and eupatorin (EUP) were chosen as a marker compounds for standardization of various O. stamineus leaf extracts. The aim was to develop and validate a new high-performance liquid chromatography (HPLC) method for quantification of 4 marker compounds (RA, TMF, SIN, EUP) in various O. stamineus leaf extracts. The method was developed and validated using RP-HPLC-diode-array detection at 320 nm for accuracy, precision and limits of detection and was applied for quantification of it markers in five different extracts prepared in solvents with increasing polarity, using a gradient mobile phase 0.1% formic acid: Acetonitrile at a flow rate of 1 ml/min on reverse phase acclaim polar advantage II C18 column (3 μm, 3 × 150 mm) with 18 min separation time. The developed method provided satisfactory precision, and the accuracy of this method was in the range of 90.2% to 105.5%. All of 4 compounds showed good linearity at R2 > 0.999. The developed method is a simple, cost effective with shorter run time (18 min) in comparison to previous methods (30 min) and utilization of environmental-friendly solvents system. Therefore, this method has the potential to replace currently used methods in the routine standardization work of O. stamineus extracts, raw materials and its commercial products.

A novel reverse phase high-performance liquid chromatography method for standardization of Orthosiphon stamineus leaf extracts

PubMed Central

Saidan, Noor Hafizoh; Aisha, Abdalrahim F.A.; Hamil, Mohd Shahrul Ridzuan; Majid, Amin Malik Shah Abdul; Ismail, Zhari

2015-01-01

Background: Orthosiphon stamineus Benth. (Lamiaceae) is a traditional medicinal plant which has been used in treating various ailments such as kidney diseases, bladder inflammation, arthritis and diabetes. The leaves contain high concentration of phenolic compounds, thus, rosmarinic acid (RA), 3’-hydroxy-5, 6, 7, 4’-tetramethoxyflavone (TMF), sinensetin (SIN) and eupatorin (EUP) were chosen as a marker compounds for standardization of various O. stamineus leaf extracts. Objective: The aim was to develop and validate a new high-performance liquid chromatography (HPLC) method for quantification of 4 marker compounds (RA, TMF, SIN, EUP) in various O. stamineus leaf extracts. Materials and Methods: The method was developed and validated using RP-HPLC-diode-array detection at 320 nm for accuracy, precision and limits of detection and was applied for quantification of it markers in five different extracts prepared in solvents with increasing polarity, using a gradient mobile phase 0.1% formic acid: Acetonitrile at a flow rate of 1 ml/min on reverse phase acclaim polar advantage II C18 column (3 μm, 3 × 150 mm) with 18 min separation time. Results: The developed method provided satisfactory precision, and the accuracy of this method was in the range of 90.2% to 105.5%. All of 4 compounds showed good linearity at R2 > 0.999. Conclusion: The developed method is a simple, cost effective with shorter run time (18 min) in comparison to previous methods (30 min) and utilization of environmental-friendly solvents system. Therefore, this method has the potential to replace currently used methods in the routine standardization work of O. stamineus extracts, raw materials and its commercial products. PMID:25598631

Effect of solvent hydrogen bonding on the photophysical properties of intramolecular charge transfer probe trans-ethyl p-(dimethylamino) cinamate and its derivative

NASA Astrophysics Data System (ADS)

Singh, T. Sanjoy; Moyon, N. S.; Mitra, Sivaprasad

2009-08-01

Intramolecular charge transfer (ICT) behavior of trans-ethyl p-(dimethylamino) cinamate (EDAC) and 4-(dimethylamino) cinnamic acid (DMACA) were studied by steady state absorption and emission, picosecond time-resolved fluorescence experiments in various pure and mixed solvent systems. The large fluorescence spectral shift in more polar solvents indicates an efficient charge transfer from the donor site to the acceptor moiety in the excited state compared to the ground state. The energy for 0,0 transition ( ν0,0) for EDAC shows very good linear correlation with static solvent dielectric property; however, fluorescence emission maximum, stokes shift and fluorescence quantum yield show significant deviation from linearity in polar protic solvents, indicating a large contribution of solvent hydrogen bonding on the excited state relaxation mechanism. A quantitative estimation of contribution from different solvatochromic parameters was made using linear free energy relationship based on Kamlet-Taft equation.

Behaviour of a solvent trapped in a physical molecular gel

NASA Astrophysics Data System (ADS)

Morfin, I.; Spagnoli, S.; Rambaud, C.; Longeville, S.; Plazanet, M.

2016-03-01

Physical gels formed by amphiphilic molecules, namely in this study Methyl-4,6-O-benzylidene-? -D-mannopyranoside, can be form either in polar and protic liquid-like water or in organic apolar solvent such as toluene. The solvent, that influences the supramolecular organization of the gelators, plays an important role in the stability and formation of the gel phase. Gelator-solvent interactions govern not only the assembly but also the solvent diffusion in the material. We present here measurements of neutron scattering (Time of Flight and Neutron Spin Echo) characterizing this microscopic behaviour. In addition, we show that transient grating spectroscopy provides valuable information through the characterization of the longitudinal acoustic wave propagating in the system. Opposite effects on the speed of sound in the gels are observed for the two solvents investigated, being relevant of the interactions between the gelators and the surrounding liquid.

Adsorption behavior of acetone solvent at the HMX crystal faces: A molecular dynamics study.

PubMed

Liu, Yingzhe; Yu, Tao; Lai, Weipeng; Ma, Yiding; Kang, Ying; Ge, Zhongxue

2017-06-01

Molecular dynamics simulations have been performed to understand the adsorption behavior of acetone (AC) solvent at the three surfaces of 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctan (HMX) crystal, i.e. (011), (110), and (020) faces. The simulation results show that the structural features and electrostatic potentials of crystal faces are determined by the HMX molecular packing, inducing distinct mass density distribution, dipole orientation, and diffusion of solvent molecules in the interfacial regions. The solvent adsorption is mainly governed by the van der Waals forces, and the crystal-solvent interaction energies among three systems are ranked as (020)≈(110)>(011). The adsorption sites for solvent incorporation at the crystal surface were found and visualized with the aid of occupancy analysis. A uniform arrangement of adsorption sites is observed at the rough (020) surface as a result of ordered adsorption motif. Copyright © 2017 Elsevier Inc. All rights reserved.

Utilizing fast multipole expansions for efficient and accurate quantum-classical molecular dynamics simulations

NASA Astrophysics Data System (ADS)

Schwörer, Magnus; Lorenzen, Konstantin; Mathias, Gerald; Tavan, Paul

2015-03-01

Recently, a novel approach to hybrid quantum mechanics/molecular mechanics (QM/MM) molecular dynamics (MD) simulations has been suggested [Schwörer et al., J. Chem. Phys. 138, 244103 (2013)]. Here, the forces acting on the atoms are calculated by grid-based density functional theory (DFT) for a solute molecule and by a polarizable molecular mechanics (PMM) force field for a large solvent environment composed of several 103-105 molecules as negative gradients of a DFT/PMM hybrid Hamiltonian. The electrostatic interactions are efficiently described by a hierarchical fast multipole method (FMM). Adopting recent progress of this FMM technique [Lorenzen et al., J. Chem. Theory Comput. 10, 3244 (2014)], which particularly entails a strictly linear scaling of the computational effort with the system size, and adapting this revised FMM approach to the computation of the interactions between the DFT and PMM fragments of a simulation system, here, we show how one can further enhance the efficiency and accuracy of such DFT/PMM-MD simulations. The resulting gain of total performance, as measured for alanine dipeptide (DFT) embedded in water (PMM) by the product of the gains in efficiency and accuracy, amounts to about one order of magnitude. We also demonstrate that the jointly parallelized implementation of the DFT and PMM-MD parts of the computation enables the efficient use of high-performance computing systems. The associated software is available online.

HOMOGENEOUS CATALYTIC OXIDATION OF HYDROCARBONS IN ALTERNATIVE SOLVENTS

EPA Science Inventory

Homogeneous Catalytic Oxidations of Hydrocarbons in Alternative Solvent Systems

Michael A. Gonzalez* and Thomas M. Becker, Sustainable Technology Division, Office of Research and Development; United States Environmental Protection Agency, 26 West Martin Luther King Drive, ...

NOVEL POLYMERIC MEMBRANE FOR DEHYDRATION OF ORGANIC SOLVENTS

EPA Science Inventory

Pervaporation has emerged as an economically viable alternative technology for dehydration of organic solvents, removal of organic compounds and organic/organic separations. Development of a membrane system with suitable flux and selectivity characteristics plays a critical role...

Spiral counter-current chromatography of small molecules, peptides and proteins using the spiral tubing support rotor.

PubMed

Knight, Martha; Finn, Thomas M; Zehmer, John; Clayton, Adam; Pilon, Aprile

2011-09-09

An important advance in countercurrent chromatography (CCC) carried out in open flow-tubing coils, rotated in planetary centrifuges, is the new design to spread out the tubing in spirals. More spacing between the tubing was found to significantly increase the stationary phase retention, such that now all types of two-phase solvent systems can be used for liquid-liquid partition chromatography in the J-type planetary centrifuges. A spiral tubing support (STS) frame with circular channels was constructed by laser sintering technology into which FEP tubing was placed in 4 spiral loops per layer from the bottom to the top and a cover affixed allowing the tubing to connect to flow-tubing of the planetary centrifuge. The rotor was mounted and run in a P.C. Inc. type instrument. Examples of compounds of molecular weights ranging from <300 to approximately 15,000 were chromatographed in appropriate two-phase solvent systems to assess the capability for separation and purification. A mixture of small molecules including aspirin was completely separated in hexane-ethyl acetate-methanol-water. Synthetic peptides including a very hydrophobic peptide were each purified to a very high purity level in a sec-butanol solvent system. In the STS rotor high stationary phase retention was possible with the aqueous sec-butanol solvent system at a normal flow rate. Finally, the two-phase aqueous polyethylene glycol-potassium phosphate solvent system was applied to separate a protein from a lysate of an Escherichia coli expression system. These experiments demonstrate the versatility of spiral CCC using the STS rotor. Copyright © 2011 Elsevier B.V. All rights reserved.

TES buffer-induced phase separation of aqueous solutions of several water-miscible organic solvents at 298.15 K: phase diagrams and molecular dynamic simulations.

PubMed

Taha, Mohamed; Lee, Ming-Jer

2013-06-28

Water and the organic solvents tetrahydrofuran, 1,3-dioxolane, 1,4-dioxane, 1-propanol, 2-propanol, tert-butanol, acetonitrile, or acetone are completely miscible in all proportions at room temperature. Here, we present new buffering-out phase separation systems that the above mentioned organic aqueous solutions can be induced to form two liquid phases in the presence of a biological buffer 2-[[1,3-dihydroxy-2-(hydroxymethyl)propan-2-yl]amino]ethanesulfonic acid (TES). The lower liquid phase is rich in water and buffer, and the upper phase is organic rich. This observation has both practical and mechanistic interests. The phase diagrams of these systems were constructed by experimental measurements at ambient conditions. Molecular dynamic (MD) simulations were performed for TES + water + THF system to understand the interactions between TES, water, and organic solvent at molecular level. Several composition-sets for this system, beyond and inside the liquid-liquid phase-splitting region, have been simulated. Interestingly, the MD simulation for compositions inside the phase separation region showed that THF molecules are forced out from the water network to start forming a new liquid phase. The hydrogen-bonds, hydrogen-bonds lifetimes, hydrogen-bond energies, radial distribution functions, coordination numbers, the electrostatic interactions, and the van der Waals interactions between the different pairs have been calculated. Additionally, MD simulations for TES + water + tert-butanol∕acetonitrile∕acetone phase separation systems were simulated. The results from MD simulations provide an explanation for the buffering-out phenomena observed in [TES + water + organic solvent] systems by a mechanism controlled by the competitive interactions of the buffer and the organic solvent with water. The molecular mechanism reported here is helpful for designing new benign separation materials.

Acidic resin-catalysed conversion of fructose into furan derivatives in low boiling point solvents.

PubMed

Zhu, Hong; Cao, Quan; Li, Chunhu; Mu, Xindong

2011-09-27

Conversion of fructose into furan derivatives 5-hydroxymethylfurfural (HMF) and 5-methoxymethylfurfural (MMF) is performed in tetrahydrofuran (THF) and methanol-organic solvent systems, catalysed by an acidic resin Amberlyst-15. The melted fructose can be converted into HMF on the surface of the solid resin catalyst in the presence of THF as an extracting phase, which is a good solvent for HMF and other by-products. The solid resin catalyst can be reused eleven times without losing its catalytic ability, with an average HMF yield of approximately 50%. Upon the addition of methanol, the generated HMF can further react with methanol to form MMF, and the total yield of HMF and MMF could be promoted to 65%. GC-MS analysis confirms the formation of a small amount of methyl levulinate in methanolorganic solvent system. Copyright © 2011 Elsevier Ltd. All rights reserved.

Method for removing hydrocarbon contaminants from solid materials

DOEpatents

Bala, Gregory A.; Thomas, Charles P.

1995-01-01

A system for removing hydrocarbons from solid materials. Contaminated solids are combined with a solvent (preferably terpene based) to produce a mixture. The mixture is washed with water to generate a purified solid product (which is removed from the system) and a drainage product. The drainage product is separated into a first fraction (consisting mostly of contaminated solvent) and a second fraction (containing solids and water). The first fraction is separated into a third fraction (consisting mostly of contaminated solvent) and a fourth fraction (containing residual solids and water). The fourth fraction is combined with the second fraction to produce a sludge which is separated into a fifth fraction (containing water which is ultimately reused) and a sixth fraction (containing solids). The third fraction is then separated into a seventh fraction (consisting of recovered solvent which is ultimately reused) and an eighth fraction (containing hydrocarbon waste).

Method for removing hydrocarbon contaminants from solid materials

DOEpatents

Bala, G.A.; Thomas, C.P.

1995-10-03

A system is described for removing hydrocarbons from solid materials. Contaminated solids are combined with a solvent (preferably terpene based) to produce a mixture. The mixture is washed with water to generate a purified solid product (which is removed from the system) and a drainage product. The drainage product is separated into a first fraction (consisting mostly of contaminated solvent) and a second fraction (containing solids and water). The first fraction is separated into a third fraction (consisting mostly of contaminated solvent) and a fourth fraction (containing residual solids and water). The fourth fraction is combined with the second fraction to produce a sludge which is separated into a fifth fraction (containing water which is ultimately reused) and a sixth fraction (containing solids). The third fraction is then separated into a seventh fraction (consisting of recovered solvent which is ultimately reused) and an eighth fraction (containing hydrocarbon waste). 4 figs.

Apparatus for removing hydrocarbon contaminants from solid materials

DOEpatents

Bala, G.A.; Thomas, C.P.

1996-02-13

A system is described for removing hydrocarbons from solid materials. Contaminated solids are combined with a solvent (preferably terpene based) to produce a mixture. The mixture is washed with water to generate a purified solid product (which is removed from the system) and a drainage product. The drainage product is separated into a first fraction (consisting mostly of contaminated solvent) and a second fraction (containing solids and water). The first fraction is separated into a third fraction (consisting mostly of contaminated solvent) and a fourth fraction (containing residual solids and water). The fourth fraction is combined with the second fraction to produce a sludge which is separated into a fifth fraction (containing water which is ultimately reused) and a sixth fraction (containing solids). The third fraction is then separated into a seventh fraction (consisting of recovered solvent which is ultimately reused) and an eighth fraction (containing hydrocarbon waste). 4 figs.

Apparatus for removing hydrocarbon contaminants from solid materials

DOEpatents

Bala, Gregory A.; Thomas, Charles P.

1996-01-01

A system for removing hydrocarbons from solid materials. Contaminated solids are combined with a solvent (preferably terpene based) to produce a mixture. The mixture is washed with water to generate a purified solid product (which is removed from the system) and a drainage product. The drainage product is separated into a first fraction (consisting mostly of contaminated solvent) and a second fraction (containing solids and water). The first fraction is separated into a third fraction (consisting mostly of contaminated solvent) and a fourth fraction (containing residual solids and water). The fourth fraction is combined with the second fraction to produce a sludge which is separated into a fifth fraction (containing water which is ultimately reused) and a sixth fraction (containing solids). The third fraction is then separated into a seventh fraction (consisting of recovered solvent which is ultimately reused) and an eighth fraction (containing hydrocarbon waste).

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

Tande, Brian; Seames, Wayne; Benson, Steve

The objective of this project was to evaluate the use of composite polymer membranes and porous membrane contactors to regenerate physical and chemical solvents for capture of carbon dioxide (CO 2) from synthesis gas or flue gas, with the goal of improving the energy efficiency of carbon capture. Both a chemical solvent (typical for a post-combustion capture of CO 2 from flue gas) and a physical solvent (typical for pre- combustion capture of CO 2 from syngas) were evaluated using two bench-scale test systems constructed for this project. For chemical solvents, polytetrafluoroethylene and polypropylene membranes were found to be ablemore » to strip CO 2 from a monoethanolamine (MEA) solution with high selectivity without significant degradation of the material. As expected, the regeneration temperature was the most significant parameter affecting the CO 2 flux through the membrane. Pore size was also found to be important, as pores larger than 5 microns lead to excessive pore wetting. For physical solvents, polydimethyl-siloxane (PDMS)-based membranes were found to have a higher CO 2 permeability than polyvinylalcohol (PVOH) based membranes, while also minimizing solvent loss. Overall, however, the recovery of CO 2 in these systems is low – less than 2% for both chemical and physical solvents – primarily due to the small surface area of the membrane test apparatus. To obtain the higher regeneration rates needed for this application, a much larger surface area would be needed. Further experiments using, for example, a hollow fiber membrane module could determine if this process could be commercially viable.« less

Volatile Solvents as Drugs of Abuse: Focus on the Cortico-Mesolimbic Circuitry

PubMed Central

Beckley, Jacob T; Woodward, John J

2013-01-01

Volatile solvents such as those found in fuels, paints, and thinners are found throughout the world and are used in a variety of industrial applications. However, these compounds are also often intentionally inhaled at high concentrations to produce intoxication. While solvent use has been recognized as a potential drug problem for many years, research on the sites and mechanisms of action of these compounds lags behind that of other drugs of abuse. In this review, we first discuss the epidemiology of voluntary solvent use throughout the world and then consider what is known about their basic pharmacology and how this may explain their use as drugs of abuse. We next present data from preclinical and clinical studies indicating that these substances induce common addiction sequelae such as dependence, withdrawal, and cognitive impairments. We describe how toluene, the most commonly studied psychoactive volatile solvent, alters synaptic transmission in key brain circuits such as the mesolimbic dopamine system and medial prefrontal cortex (mPFC) that are thought to underlie addiction pathology. Finally, we make the case that activity in mPFC circuits is a critical regulator of the mesolimbic dopamine system's ability to respond to volatile solvents like toluene. Overall, this review provides evidence that volatile solvents have high abuse liability because of their selective effects on critical nodes of the addiction neurocircuitry, and underscores the need for more research into how these compounds induce adaptations in neural circuits that underlie addiction pathology. PMID:23954847