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.

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.

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.

3D investigation on polystyrene colloidal crystals by floatage self-assembly with mixed solvent via synchrotron radiation x-ray phase-contrast computed tomography

NASA Astrophysics Data System (ADS)

Fu, Yanan; Xie, Honglan; Deng, Biao; Du, Guohao; Xiao, Tiqiao

2017-06-01

The floatage self-assembly method was introduced with mixed solvent as the medium of polystyrene sphere suspension to fabricate the colloidal crystal. The three dimensional (3D) void system of the colloidal crystal was noninvasively characterized by synchrotron radiation phase-contrast computed tomography, and the quantitative image analysis was implemented aiming to the polystyrene sphere colloidal crystal. Comparing with gravity sedimentation method, the three samples fabricated from floatage self-assembly with mixed solvents have the lowest porosity, and when ethylene glycol and water were mixed with ratio of 1:1, the lowest porosity of 27.49% could be achieved, that has been very close to the minimum porosity of ordered 3D monodisperse sphere array (26%). In single slices, the porosities and fractal dimension for the voids were calculated. The results showed that two factors would significantly influence the porosity of the whole colloidal crystal: the first deposited sphere layer's orderliness and the sedimentation speed of the spheres. The floatage self-assembly could induce a stable close-packing process, resulted from the powerful nucleation force-lateral capillary force coupled with the mixed solvent to regulate the floating upward speed for purpose of matching the assembly rate.

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.

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.

Influence of sample processing on the analysis of carotenoids in maize.

PubMed

Rivera, Sol; Canela, Ramon

2012-09-21

We performed a number of tests with the aim to develop an effective extraction method for the analysis of carotenoid content in maize seed. Mixtures of methanol-ethyl acetate (6:4, v/v) and methanol-tetrahydrofuran (1:1, v/v) were the most effective solvent systems for carotenoid extraction from maize endosperm under the conditions assayed. In addition, we also addressed sample preparation prior to the analysis of carotenoids by liquid chromatography (LC). The LC response of extracted carotenoids and standards in several solvents was evaluated and results were related to the degree of solubility of these pigments. Three key factors were found to be important when selecting a suitable injection solvent: compatibility between the mobile phase and injection solvent, carotenoid polarity and content in the matrix.

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

PubMed Central

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

2014-01-01

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

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.

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.

Molecular-level comparison of alkylsilane and polar-embedded reversed-phase liquid chromatography systems.

PubMed

Rafferty, Jake L; Siepmann, J Ilja; Schure, Mark R

2008-08-15

Stationary phases with embedded polar groups possess several advantages over conventional alkylsilane phases, such as reduced peak tailing, enhanced selectivity for specific functional groups, and the ability to use a highly aqueous mobile phase. To gain a deeper understanding of the retentive properties of these reversed-phase packings, molecular simulations were carried out for three different stationary phases in contact with mobile phases of various water/methanol ratios. Two polar-embedded phases were modeled, namely, amide and ether containing, and compared to a conventional octadecylsilane phase. The simulations show that, due to specific hydrogen bond interactions, the polar-embedded phases take up significantly more solvent and are more ordered than their alkyl counterparts. Alkane and alcohol probe solutes indicate that the polar-embedded phases are less retentive than alkyl phases for nonpolar species, whereas polar species are more retained by them due to hydrogen bonding with the embedded groups and the increased amount of solvent within the stationary phase. This leads to a significant reduction of the free-energy barrier for the transfer of polar species from the mobile phase to residual silanols, and this reduced barrier provides a possible explanation for reduced peak tailing.

Additives and solvents-induced phase and morphology modification of NaYF{sub 4} for improving up-conversion emission

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

Zhuang, Jianle, E-mail: zhuangjianle@126.com; MOE Key Laboratory of Bioinorganic and Synthetic Chemistry, School of Chemistry and Chemical Engineering, Sun Yat-Sen University, Guangzhou 510275; Yang, Xianfeng

Both cubic and hexagonal NaYF{sub 4} were synthesized in different reaction systems via hydro/solvo-thermal route. The effects of reaction temperature, solvents, and additives on the synthesis of NaYF{sub 4} have been studied in detail. It has been shown that phase transformation from cubic NaYF{sub 4} to hexagonal NaYF{sub 4} always occurred. The sequence of the ability for inducing the phase transformation was ethanol>H{sub 2}O>acetic acid. It is found that ethanol can not only facilitate the formation of hexagonal NaYF{sub 4} but also control the growth of the crystal. This is quite unusual for the growth of H-NaYF{sub 4}. The up-conversionmore » emission properties of Yb/Er co-doped NaYF{sub 4} have also been investigated and the results demonstrated some general principles for improving up-conversion emission. - Graphical abstract: Additives and solvents can induce the phase transformation of NaYF{sub 4}, typically the use of organic sodium salt and ethanol. - Highlights: • The effect of additives and solvents on the synthesis of NaYF{sub 4} was studied in detail. • Ethanol can facilitate the formation of H-NaYF{sub 4} while acetic acid restrain it. • Three general principles for improving up-conversion emission were summarized.« less

Multiphase flow modeling in centrifugal partition chromatography.

PubMed

Adelmann, S; Schwienheer, C; Schembecker, G

2011-09-09

The separation efficiency in Centrifugal Partition Chromatography (CPC) depends on selection of a suitable biphasic solvent system (distribution ratio, selectivity factor, sample solubility) and is influenced by hydrodynamics in the chambers. Especially the stationary phase retention, the interfacial area for mass transfer and the flow pattern (backmixing) are important parameters. Their relationship with physical properties, operating parameters and chamber geometry is not completely understood and predictions are hardly possible. Experimental flow visualization is expensive and two-dimensional only. Therefore we simulated the flow pattern using a volume-of-fluid (VOF) method, which was implemented in OpenFOAM®. For the three-dimensional simulation of a rotating FCPC®-chamber, gravitational centrifugal and Coriolis forces were added to the conservation equation. For experimental validation the flow pattern of different solvent systems was visualized with an optical measurement system. The amount of mobile phase in a chamber was calculated from gray scale values of videos recorded by an image processing routine in ImageJ®. To visualize the flow of the stationary phase polyethylene particles were used to perform a qualitative particle image velocimetry (PIV) analysis. We found a good agreement between flow patterns and velocity profiles of experiments and simulations. By using the model we found that increasing the chamber depth leads to higher specific interfacial area. Additionally a circular flow in the stationary phase was identified that lowers the interfacial area because it pushes the jet of mobile phase to the chamber wall. The Coriolis force alone gives the impulse for this behavior. As a result the model is easier to handle than experiments and allows 3D prediction of hydrodynamics in the chamber. Additionally it can be used for optimizing geometry and operating parameters for given physical properties of solvent systems. Copyright © 2011 Elsevier B.V. All rights reserved.

DIFFUSED SOLUTE-SOLVENT INTERFACE WITH POISSON-BOLTZMANN ELECTROSTATICS: FREE-ENERGY VARIATION AND SHARP-INTERFACE LIMIT.

PubMed

Li, B O; Liu, Yuan

A phase-field free-energy functional for the solvation of charged molecules (e.g., proteins) in aqueous solvent (i.e., water or salted water) is constructed. The functional consists of the solute volumetric and solute-solvent interfacial energies, the solute-solvent van der Waals interaction energy, and the continuum electrostatic free energy described by the Poisson-Boltzmann theory. All these are expressed in terms of phase fields that, for low free-energy conformations, are close to one value in the solute phase and another in the solvent phase. A key property of the model is that the phase-field interpolation of dielectric coefficient has the vanishing derivative at both solute and solvent phases. The first variation of such an effective free-energy functional is derived. Matched asymptotic analysis is carried out for the resulting relaxation dynamics of the diffused solute-solvent interface. It is shown that the sharp-interface limit is exactly the variational implicit-solvent model that has successfully captured capillary evaporation in hydrophobic confinement and corresponding multiple equilibrium states of underlying biomolecular systems as found in experiment and molecular dynamics simulations. Our phase-field approach and analysis can be used to possibly couple the description of interfacial fluctuations for efficient numerical computations of biomolecular interactions.

Effect of high pressure homogenization on aqueous phase solvent extraction of lipids from Nannochloris Oculata microalgae

DOE PAGES

Samarasinghe, Nalin; Fernando, Sandun; Faulkner, William B.

2012-12-01

The ability to extract lipids from high-moisture Nannochloris Oculata algal biomass disrupted with high pressure homogenization was investigated. During the first phase, the effect of high pressure homogenization (system pressure and number of passes) on disrupting aqueous algae (of different concentrations and degree of stress) was investigated. Secondly, the effect of degree of cell wall disruption on the amount of lipids extracted with three solvents, namely: hexane, dichloromethane and chloroform, were compared. Studies reveled that high pressure homogenization is effective on cell disruption while the amount of system pressure being the most significant factor affecting the degree of cell breakage.more » Although the number of passes had some impact, the level of disruption seemed to level-off after a certain number of passes. The study revealed that slightly polar solvents (such as chloroform and dichloromethane) performed better in aqueous-phase lipid extractions as compared to hexane. Also, it was revealed that it was not necessary to disrupt the algal cells completely to achieve appreciable levels of lipid yields. In fact, conditions that exerted only 20% of the cells to completely disrupt, allowed sufficient damage to liberate most of the lipids contained in the remainder of the cells.« less

Effect of high pressure homogenization on aqueous phase solvent extraction of lipids from Nannochloris Oculata microalgae

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

Samarasinghe, Nalin; Fernando, Sandun; Faulkner, William B.

The ability to extract lipids from high-moisture Nannochloris Oculata algal biomass disrupted with high pressure homogenization was investigated. During the first phase, the effect of high pressure homogenization (system pressure and number of passes) on disrupting aqueous algae (of different concentrations and degree of stress) was investigated. Secondly, the effect of degree of cell wall disruption on the amount of lipids extracted with three solvents, namely: hexane, dichloromethane and chloroform, were compared. Studies reveled that high pressure homogenization is effective on cell disruption while the amount of system pressure being the most significant factor affecting the degree of cell breakage.more » Although the number of passes had some impact, the level of disruption seemed to level-off after a certain number of passes. The study revealed that slightly polar solvents (such as chloroform and dichloromethane) performed better in aqueous-phase lipid extractions as compared to hexane. Also, it was revealed that it was not necessary to disrupt the algal cells completely to achieve appreciable levels of lipid yields. In fact, conditions that exerted only 20% of the cells to completely disrupt, allowed sufficient damage to liberate most of the lipids contained in the remainder of the cells.« less

Comprehensive two-dimensional normal-phase liquid chromatography × reversed-phase liquid chromatography for analysis of toad skin.

PubMed

Li, Jia-Fu; Yan, Xia; Wu, Yun-Long; Fang, Mei-Juan; Wu, Zhen; Qiu, Ying-Kun

2017-04-15

An analytical two-dimensional normal-phase liquid chromatography × reversed-phase liquid chromatography (2D NPLC × RPLC) system was constructed with a newly developed thermal evaporation assisted adsorption (TEAA) interface. This novel TEAA interface with heating temperature above solvent boiling point allowed fast removal of organic NPLC solvent and successfully solved the solvent incompatibility problem between NPLC and RPLC. The system achieved rapid on-line solvent exchange between the two dimensions within a short modulation time of 190 s and was applied in the analysis of an extract from the skin of Bufo bufo gargarizans. This is the first time to realize the on-line comprehensive analysis of a moderate polar natural product by coupling NPLC with reversed phase ultra-high performance liquid chromatography (UHPLC). To be highlighted, with the TEAA interface, the 2D NPLC × RPLC system provided excellent resolution and orthogonality (75.2%), when compared with that of 2D RPLC × RPLC. Copyright © 2017 Elsevier B.V. All rights reserved.

Data in support of three phase partitioning of zingibain, a milk-clotting enzyme from Zingiber officinale Roscoe rhizomes

PubMed Central

Gagaoua, Mohammed; Hafid, Kahina; Hoggas, Naouel

2016-01-01

This paper describes data related to a research article titled “Three Phase Partitioning of zingibain, a milk-clotting enzyme from Zingiber officinale Roscoe rhizomes” (Gagaoua et al., 2015) [1]. Zingibain (EC 3.4.22.67), is a coagulant cysteine protease and a meat tenderizer agent that have been reported to produce satisfactory final products in dairy and meat technology, respectively. Zingibains were exclusively purified using chromatographic techniques with very low yield purification. This paper includes data of the effect of temperature, usual salts and organic solvents on the efficiency of the three phase partitioning (TPP) system. Also it includes data of the kinetic activity characterization of the purified zingibain using TPP purification approach. PMID:26909379

Discrete and continuum modeling of solvent effects in a twisted intramolecular charge transfer system: The 4-N,N-dimethylaminobenzonitrile (DMABN) molecule.

PubMed

Modesto-Costa, Lucas; Borges, Itamar

2018-08-05

The 4-N,N-dimethylaminobenzonitrile (DMABN) molecule is a prototypical system displaying twisted intramolecular (TICT) charge transfer effects. The ground and the first four electronic excited states (S 1 -S 4 ) in gas phase and upon solvation were studied. Charge transfer values as function of the torsion angle between the donor group (dimethylamine) and the acceptor moiety (benzonitrile) were explicitly computed. Potential energy curves were also obtained. The algebraic diagrammatic construction method at the second-order [ADC(2)] ab initio wave function was employed. Three solvents of increased polarities (benzene, DMSO and water) were investigated using discrete (average solvent electrostatic configuration - ASEC) and continuum (conductor-like screening model - COSMO) models. The results for the S 3 and S 4 excited states and the S 1 -S 4 charge transfer curves were not previously available in the literature. Electronic gas phase and solvent vertical spectra are in good agreement with previous theoretical and experimental results. In the twisted (90°) geometry the optical oscillator strengths have negligible values even for the S 2 bright state. Potential energy curves show two distinct pairs of curves intersecting at decreasing angles or not crossing in the more polar solvents. Charge transfer and electric dipole values allowed the rationalization of these results. The former effects are mostly independent of the solvent model and polarity. Although COSMO and ASEC solvent models mostly lead to similar results, there is an important difference: some crossings of the excitation energy curves appear only in the ASEC solvation model, which has important implications to the photochemistry of DMABN. Copyright © 2018 Elsevier B.V. All rights reserved.

Lyotropic Phase Behavior of Polybutadiene-Poly(ethylene oxide) Diblock Copolymers in Ionic Liquids

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

Simone, Peter M.; Lodge, Timothy P.

2008-08-26

The lyotropic phase behavior of three poly(1,2-butadiene-b-ethylene oxide) diblock copolymers (PB-PEO) with different monomer volume fractions has been studied in two different ionic liquids, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMI][TFSI]) and 1-butyl-3-methylimidazolium hexafluorophosphate ([BMI][PF{sub 6}]), across the complete concentration range. The ordered microstructures present in the solutions were characterized via small-angle X-ray scattering (SAXS). The phase diagrams for the PB-PEO/ionic liquid solutions include regions corresponding to the classical copolymer microstructures: body-centered-cubic lattices of spheres, hexagonally ordered cylinders, and lamellae. Additionally, the phase diagrams also include wide regions of coexisting microstructures and regions apparently corresponding to a disordered network microstructure. The phase behavior ofmore » the PB-PEO copolymers in both ionic liquids was comparable to their previously reported aqueous solution behavior. The temperature dependence of the phase diagrams was very modest, indicative of a highly segregated system. The level of solvent selectivity was also investigated via cryogenic transmission electron microscopy (cryo-TEM) on dilute solutions. On the basis of the morphology of the dilute solution copolymer aggregate structures in the ionic liquid solvents, and on the structural length scales of the concentrated solutions, it was concluded that for PB-PEO [BMI][PF{sub 6}] behaves as a more selective solvent than [EMI][TFSI].« less

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

PubMed

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

2013-06-28

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

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.

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

PubMed

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

2006-01-01

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

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.

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.

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.

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

PubMed

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

2016-07-22

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

Investigation of aggregation in solvent extraction of lanthanides by acidic extractants (organophosphorus and naphthenic acid)

USGS Publications Warehouse

Zhou, N.; Wu, J.; Yu, Z.; Neuman, R.D.; Wang, D.; Xu, G.

1997-01-01

Three acidic extractants (I) di(2-ethylhexyl) phosphoric acid (HDEHP), (II) 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester (HEHPEHE) and (III) naphthenic acid were employed in preparing the samples for the characterization of the coordination structure of lanthanide-extractant complexes and the physicochemical nature of aggregates formed in the organic diluent of the solvent extraction systems. Photo correlation spectroscopy (PCS) results on the aggregates formed by the partially saponified HDEHP in n-heptane showed that the hydrodynamic radius of the aggregates was comparable to the molecular dimensions of HDEHP. The addition of 2-octanol into the diluent, by which the mixed solvent was formed, increased the dimensions of the corresponding aggregates. Aggregates formed from the lanthanide ions and HDEHP in the organic phase of the extraction systems were found very unstable. In the case of naphthenic acid, PCS data showed the formation of w/o microemulsion from the saponified naphthenic acid in the mixed solvent. The extraction of lanthanides by the saponified naphthenic acid in the mixed solvent under the given experimental conditions was a process of destruction of the w/o microemulsion. A possible mechanism of the breakdown of the w/o microemulsion droplets is discussed.

Bench Scale Process for Low Cost CO 2 Capture Using a PhaseChanging Absorbent: Techno-Economic Analysis Topical Report

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

Miebach, Barbara; McDuffie, Dwayne; Spiry, Irina

The objective of this project is to design and build a bench-scale process for a novel phase-changing CO 2 capture solvent. The project will establish scalability and technical and economic feasibility of using a phase-changing CO 2 capture absorbent for post-combustion capture of CO 2 from coal-fired power plants with 90% capture efficiency and 95% CO 2 purity at a cost of $40/tonne of CO 2 captured by 2025 and a cost of <$10/tonne of CO 2 captured by 2035. This report presents system and economic analysis for a process that uses a phase changing aminosilicone solvent to remove COmore » 2 from pulverized coal (PC) power plant flue gas. The aminosilicone solvent is a pure 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane (GAP-0). Performance of the phase-changing aminosilicone technology is compared to that of a conventional carbon capture system using aqueous monoethanolamine (MEA). This analysis demonstrates that the aminosilicone process has significant advantages relative to an MEA-based system. The first-year CO 2 removal cost for the phase-changing CO 2 capture process is $52.1/tonne, compared to $66.4/tonne for the aqueous amine process. The phase-changing CO 2 capture process is less costly than MEA because of advantageous solvent properties that include higher working capacity, lower corrosivity, lower vapor pressure, and lower heat capacity. The phase-changing aminosilicone process has approximately 32% lower equipment capital cost compared to that of the aqueous amine process. However, this solvent is susceptible to thermal degradation at CSTR desorber operating temperatures, which could add as much as $88/tonne to the CO 2 capture cost associated with solvent makeup. Future work is focused on mitigating this critical risk by developing an advanced low-temperature desorber that can deliver comparable desorption performance and significantly reduced thermal degradation rate.« less

Sugaring-out extraction of acetoin from fermentation broth by coupling with fermentation.

PubMed

Dai, Jian-Ying; Ma, Lin-Hui; Wang, Zhuang-Fei; Guan, Wen-Tian; Xiu, Zhi-Long

2017-03-01

Acetoin is a natural flavor and an important bio-based chemical which could be separated from fermentation broth by solvent extraction, salting-out extraction or recovered in the form of derivatives. In this work, a novel method named as sugaring-out extraction coupled with fermentation was tried in the acetoin production by Bacillus subtilis DL01. The effects of six solvents on bacterial growth and the distribution of acetoin and glucose in different solvent-glucose systems were explored. The operation parameters such as standing time, glucose concentration, and volume ratio of ethyl acetate to fermentation broth were determined. In a system composed of fermentation broth, glucose (100%, m/v) and two-fold volume of ethyl acetate, nearly 100% glucose was distributed into bottom phase, and 61.2% acetoin into top phase without coloring matters and organic acids. The top phase was treated by vacuum distillation to remove solvent and purify acetoin, while the bottom phase was used as carbon source to produce acetoin in the next batch of fermentation.

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.

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.

Size exclusion chromatographic analysis of refuse-derived fuel for mycotoxins

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

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

1980-11-01

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

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

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

PubMed

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

2015-12-01

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

Influence of physical properties and operating parameters on hydrodynamics in Centrifugal Partition Chromatography.

PubMed

Adelmann, S; Schembecker, G

2011-08-12

Besides the selection of a suitable biphasic solvent system the separation efficiency in Centrifugal Partition Chromatography (CPC) is mainly influenced by the hydrodynamics in the chambers. The flow pattern, the stationary phase retention and the interfacial area for mass transfer strongly depend on physical properties of the solvent system and operating parameters. In order to measure these parameters we visualized the hydrodynamics in a FCPC-chamber for five different solvent systems with an optical measurement system and calculated the stationary phase retention, interfacial area and the distribution of mobile phase thickness in the chamber. Although inclined chambers were used we found that the Coriolis force always deflected the mobile phase towards the chamber wall reducing the interfacial area. This effect increased for systems with low density difference. We also have shown that the stability of phase systems (stationary phase retention) and its tendency to disperse increased for smaller values of the ratio of interfacial tension and density difference. But also the viscosity ratio and the flow pattern itself had a significant effect on retention and dispersion of the mobile phase. As a result operating parameters should be chosen carefully with respect to physical properties for a CPC system. In order to reduce the effect of the Coriolis force CPC devices with greater rotor radius are desirable. Copyright © 2011 Elsevier B.V. All rights reserved.

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

Alginate as immobilization matrix and stabilizing agent in a two-phase liquid system: application in lipase-catalysed reactions.

PubMed

Hertzberg, S; Kvittingen, L; Anthonsen, T; Skjåk-Braek, G

1992-01-01

Alginate was evaluated as an immobilization matrix for enzyme-catalyzed reactions in organic solvents. In contrast to most hydrogels, calcium alginate was found to be stable in a range of organic solvents and to retain the enzyme inside the gel matrix. In hydrophobic solvents, the alginate gel (greater than 95% water) thus provided a stable, two-phase liquid system. The lipase from Candida cylindracea, after immobilization in alginate beads, catalysed esterification and transesterification in n-hexane under both batch and continuous-flow conditions. The operational stability of the lipase was markedly enhanced by alginate entrapment. In the esterification of butanoic acid with n-butanol, better results were obtained in the typical hydrophilic calcium alginate beads than in less hydrophilic matrices. The effects of substrate concentration, matrix area, and polarity of the substrate alcohols and of the organic solvent on the esterification activity were examined. The transesterification of octyl 2-bromopropanoate with ethanol was less efficient than that of ethyl 2-bromopropanoate with octanol. By using the hydrophilic alginate gel as an immobilization matrix in combination with a mobile hydrophobic phase, a two-phase liquid system was achieved with definite advantages for a continuous, enzyme-catalysed process.

Configurations and Dynamics of Semi-Flexible Polymers in Good and Poor Solvents

NASA Astrophysics Data System (ADS)

Larson, Ronald

We develop coarse-graining procedures for determining the conformational and dynamic behavior of semi-flexible chains with and without flow using Brownian dynamics (BD) simulations that are insensitive to the degree of coarse-graining. In the absence of flow, in a poor solvent, we find three main collapsed states: torus, bundle, and globule over a range of dimensionless ratios of the three energy parameters, namely solvent-polymer surface energy, energy of polymer folds, and polymer bending energy or persistence length. A theoretical phase diagram, confirmed by BD simulations, captures the general phase behavior of a single long chain (>10 Kuhn lengths) at moderately high (order unity) dimensionless temperature, which is the ratio of thermal energy to the attractive interaction between neighboring monomers. We also find converged results for polymer conformations in shear or extensional flow in solvents of various qualities and determine scaling laws for chain dimensions for low, moderate, and high Weissenberg numbers Wi. We also derive scaling laws to describe chains dimensions and tumbling rates in these regimes.

Evaluation of the separation performance of polyvinylpyrrolidone as a virtual stationary phase for chromatographic NMR.

PubMed

Huang, Shaohua; Wu, Rui; Bai, Zhengwu; Yang, Ying; Li, Suying; Dou, Xiaowei

2014-09-01

Polyvinylpyrrolidone (PVP) was used as a virtual stationary phase to separate p-xylene, benzyl alcohol, and p-methylphenol by the chromatographic NMR technique. The effects of concentration and weight-average molecular weight (Mw) of PVP, solvent viscosity, solvent polarity, and sample temperature on the resolution of these components were investigated. It was found that both higher PVP concentration and higher PVP Mw caused the increase of diffusion resolution for the three components. Moreover, the diffusion resolution did not change at viscosity-higher solvents. Moreover, the three components showed different resolution at different solvents. As temperature increased, the diffusion resolution between p-xylene and benzyl alcohol gradually increased, and the one between p-xylene and p-methylphenol slightly increased from 278 to 298 K and then decreased above 298 K. It was also found that the polarity of the analytes played an important role for the separation by affecting the diffusion coefficient. Copyright © 2014 John Wiley & Sons, Ltd.

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.

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.

A theoretical thermochemical study of solute-solvent dielectric effects in the displacement of codon-anticodon base pairs

NASA Astrophysics Data System (ADS)

Monajjemi, M.; Razavian, M. H.; Mollaamin, F.; Naderi, F.; Honarparvar, B.

2008-12-01

Quantum-chemical solvent effect theories describe the electronic structure of a molecular subsystem embedded in a solvent or other molecular environment. The solvation of biomolecules is important in molecular biology, since numerous processes involve proteins interacting in changing solvent-solute systems. In this theoretical study, we focus on mRNA-tRNA base pairs as a fundamental step in protein synthesis influenced by hydrogen bonding between two antiparallel trinucleotides, namely, the mRNA codon and tRNA anticodon. We use the mean reaction field theories, which describe electrostatic and polarization interactions between solute and solvent in the AAA, UUU, AAG, and UUC triplex sequences optimized in various solvent media such as water, dimethylsulfoxide, methanol, ethanol, and cyclopean using the self-consistent reaction field model. This process depends on either the reaction potential function of the solvent or charge transfer operators that appear in solute-solvent interaction. Because of codon and anticodon biological criteria, we performed nonempirical quantum-mechanical calculations at the BLYP and B3LYP/3-21G, 6-31G, and 6-31G* levels of theory in the gas phase and five solvents at three temperatures. Finally, to obtain more information, we calculated thermochemical parameters to find that the dielectric constant of solvents plays an important role in the displacement of amino acid sequences on codon-anticodon residues in proteins, which can cause some mutations in humans.

Comparison of the peak resolution and the stationary phase retention between the satellite and the planetary motions using the coil satellite centrifuge with counter-current chromatographic separation of 4-methylumbelliferyl sugar derivatives.

PubMed

Shinomiya, Kazufusa; Zaima, Kazumasa; Harada, Yukina; Yasue, Miho; Harikai, Naoki; Tokura, Koji; Ito, Yoichiro

2017-01-20

Coil satellite centrifuge (CSC) produces the complex satellite motion consisting of the triplicate rotation of the coiled column around three axes including the sun axis (the angular velocity, ω 1 ), the planet axis (ω 2 ) and the satellite axis (the central axis of the column) (ω 3 ) according to the following formula: ω 1 =ω 2 +ω 3 . Improved peak resolution in the separation of 4-methylumbelliferyl sugar derivatives was achieved using the conventional multilayer coiled columns with ethyl acetate/1-butanol/water (3: 2: 5, v/v) for the lower mobile phase at the combination of the rotation speeds (ω 1 , ω 2 , ω 3 )=(300, 150, 150rpm), and (1:4:5, v/v) for the upper mobile phase at (300:100:200rpm). The effect of the satellite motion on the peak resolution and the stationary phase retention was evaluated by each CSC separation with the different rotation speeds of ω 2 and ω 3 under the constant revolution speed at ω 1 =300rpm. With the lower mobile phase, almost constant peak resolution and stationary phase retention were yielded regardless of the change of ω 2 and ω 3 , while with the upper mobile phase these two values were sensitively varied according to the different combination of ω 2 and ω 3 . For example, when ω 2 =147 or 200rpm is used, no stationary phase was retained in the coiled column while ω 2 =150rpm could retain enough volume of stationary phase for separation. On the other hand, the combined rotation speeds at (ω 1 , ω 2 , ω 3 )=(300, 300, 0rpm) or (300, 0, 300rpm) produced insufficient peak resolution regardless of the choice of the mobile phase apparently due to the lack of rotation speed except at (300, 0, 300rpm) with the upper mobile phase. At lower rotation speed of ω 1 =300rpm, better peak resolution and stationary phase retention were obtained by the satellite motion (ω 3 ) than by the planetary motion (ω 2 ), or ω 3 >ω 2 . The effect of the hydrophobicity of the two-phase solvent systems on the stationary phase retention was further examined using the n-hexane/ethyl acetate/1-butanol/methanol/water system at different volume ratios. In the satellite motion at (ω 1 , ω 2 , ω 3 )=(300, 150, 150rpm), almost constant stationary phase retention was obtained with the lower mobile phase regardless of the hydrophobicity of the solvent system whereas the stationary phase retention varied according to the volume ratio of the two-phase solvent system for the upper mobile phase. However, stable stationary phase retention was observed with either phase used as the mobile phase. In order to analyze the acceleration acting on the coiled column, an acceleration sensor was set on the column holder by displacing the multilayer column. The combination of the rotation speeds at (300, 100, 200rpm) showed double loops in the acceleration track, whereas (300, 150, 150rpm) showed a single loop, and all other combinations showed, complex tracks. The overall results indicate that the satellite motion is seriously affected by the combination of rotation speeds and the hydrophobicity of the two-phase solvent system when the upper phase was used as the mobile phase for separation. Copyright © 2016 Elsevier B.V. All rights reserved.

Comparison of the peak resolution and the stationary phase retention between the satellite and the planetary motions using the coil satellite centrifuge with counter-current chromatographic separation of 4-methylumbelliferyl sugar derivatives

PubMed Central

Shinomiya, Kazufusa; Zaima, Kazumasa; Harada, Yukina; Yasue, Miho; Harikai, Naoki; Tokura, Koji; Ito, Yoichiro

2016-01-01

Coil satellite centrifuge (CSC) produces the complex satellite motion consisting of the triplicate rotation of the coiled column around three axes including the sun axis (the angular velocity, ω1), the planet axis (ω2) and the satellite axis (the central axis of the column) (ω3) according to the following formula: ω1 = ω2 + ω3. Improved peak resolution in the separation of 4-methylumbelliferyl sugar derivatives was achieved using the conventional multilayer coiled columns with ethyl acetate/1-butanol/water (3 : 2 : 5, v/v) for the lower mobile phase at the combination of the rotation speeds (ω1, ω2, ω3) = (300, 150, 150 rpm), and (1 : 4 : 5, v/v) for the upper mobile phase at (300 : 100 : 200 rpm). The effect of the satellite motion on the peak resolution and the stationary phase retention was evaluated by each CSC separation with the different rotation speeds of ω2 and ω3 under the constant revolution speed at ω1 = 300 rpm. With the lower mobile phase, almost constant peak resolution and stationary phase retention were yielded regardless of the change of ω2 and ω3, while with the upper mobile phase these two values were sensitively varied according to the different combination of ω2 and ω3. For example, when ω2 = 147 or 200 rpm is used, no stationary phase was retained in the coiled column while ω2 = 150 rpm could retain enough volume of stationary phase for separation. On the other hand, the combined rotation speeds at (ω1, ω2, ω3) = (300, 300, 0 rpm) or (300, 0, 300 rpm) produced insufficient peak resolution regardless of the choice of the mobile phase apparently due to the lack of rotation speed except at (300, 0, 300 rpm) with the upper mobile phase. At lower rotation speed of ω1 = 300 rpm, better peak resolution and stationary phase retention were obtained by the satellite motion (ω3) than by the planetary motion (ω2), or ω3 > ω2. The effect of the hydrophobicity of the two-phase solvent systems on the stationary phase retention was further examined using the n-hexane/ethyl acetate/1-butanol/methanol/water system at different volume ratios. In the satellite motion at (ω1, ω2, ω3) = (300, 150, 150 rpm), almost constant stationary phase retention was obtained with the lower mobile phase regardless of the hydrophobicity of the solvent system whereas the stationary phase retention varied according to the volume ratio of the two-phase solvent system for the upper mobile phase. However, stable stationary phase retention was observed with either phase used as the mobile phase. In order to analyze the acceleration acting on the coiled column, an acceleration sensor was set on the column holder by displacing the multilayer column. The combination of the rotation speeds at (300, 100, 200 rpm) showed double loops in the acceleration track, whereas (300, 150, 150 rpm) showed a single loop, and all other combinations showed, complex tracks. The overall results indicate that the satellite motion is seriously affected by the combination of rotation speeds and the hydrophobicity of the two-phase solvent system when the upper phase was used as the mobile phase for separation. PMID:28040269

Determination of thermodynamic properties of isotactic poly(1-butene) at infinite dilution using density and inverse gas chromatography.

PubMed

Kozłowska, Marta Karolina; Domańska, Urszula; Lempert, Małgorzata; Rogalski, Marek

2005-03-18

The partial molar volumes, V1(M), and the molar volume of isotactic crystalline low-molecular-weight poly(1-butene), iPBu-1, V1, have been calculated from the measured density of {iPBu-1 + solvent (n-hexane, n-heptane, n-nonane, n-decane, p-xylene, cyclohexane and chloroform)} systems. Some of the thermodynamic quantities were also obtained for the iPBu-1 with eight hydrocarbons (n-octane, n-decane, n-undecane, n-dodecane, n-tridecane, o-xylene, m-xylene, p-xylene) by the method of inverse gas chromatography at various temperatures. The weight fraction activity coefficients of the solvent at infinite dilution, omega2(infinity) and the Flory-Huggins thermodynamic interaction parameters, chi21(infinity), between polymer and solvents were determined. The partial molar free energy, deltaG2(infinity), the partial molar heat of mixing, deltaH2(infinity), at infinite dilution and the polymer solubility parameter, delta1, were calculated. Additionally, the (solid + liquid) binary mixtures equilibria, SLE, of iPBu-1 with three hydrocarbons (n-octane, n-decane and m-xylene) were studied by a dynamic method. By performing these experiments over a large concentration range, the T-x phase diagrams of the polymer-solvent systems were constructed. The excess Gibbs energy models were used to describe the nonideal behaviour of the liquid phase. The omega2(infinity) were determined from the solubility measurements and were predicted by using the UNIFAC FV model.

Solvent history dependence of gramicidin A conformations in hydrated lipid bilayers.

PubMed Central

LoGrasso, P V; Moll, F; Cross, T A

1988-01-01

Reconstituted lipid bilayers of dimyristoylphosphatidylcholine (DMPC) and gramicidin A' have been prepared by cosolubilizing gramicidin and DMPC in one of three organic solvent systems followed by vacuum drying and hydration. The conformational state of gramicidin as characterized by 23Na NMR, circular dichroism, and solid state 15N NMR is dependent upon the cosolubilizing solvent system. In particular, two conformational states are described; a state in which Na+ has minimal interactions with the polypeptide, referred to as a nonchannel state, and a state in which Na+ interacts very strongly with the polypeptide, referred to as the channel state. Both of these conformations are intimately associated with the hydrophobic core of the lipid bilayer. Furthermore, both of these states are stable in the bilayer at neutral pH and at a temperature above the bilayer phase transition temperature. These results with gramicidin suggest that the conformation of membrane proteins may be dictated by the conformation before membrane insertion and may be dependent upon the mechanism by which the insertion is accomplished. PMID:2462923

Quantitative analysis of psilocybin and psilocin in psilocybe baeocystis (Singer and Smith) by high-performance liquid chromatography and by thin-layer chromatography.

PubMed

Beug, M W; Bigwood, J

1981-03-27

Rapid quantification of psilocybin and psilocin in extracts of wild mushrooms is accomplished by reversed-phase high-performance liquid chromatography with paired-ion reagents. Nine solvent systems and three solid supports are evaluated for their efficiency in separating psilocybin, psilocin and other components of crude mushroom extracts by thin-layer chromatography.

Effect of solvents on the optical and morphological properties of MEH-PPV: PC70BM nanocomposites

NASA Astrophysics Data System (ADS)

Mhamdi, Asya; Ltaief, Adnen; Bouazizi, Abdelaziz

2017-10-01

Focused on phase separation and morphologies of polymer poly [2-methoxy-5-(2'-ethyl) hexoxy-1,4-phenylenevinylene] (MEH-PPV) and [6,6]-phenylC71-butyric acid methyl ester (PC70BM) nanocomposite, we studied the effect of organic solvent on the optical and morphological properties of these blends. The MEH-PPV: PC70BM films was prepared using three different solvent; Tetrahydrofuran (THF), Chlorobenzene (CB) and Toluene. On the other hand, the effect of 1-8 octanedithiol additives is also studied with the same different solvents. These blend films are characterized by photoluminescence spectroscopy, UV-Vis absorption spectroscopy and atomic force microscopy (AFM). The photoluminescence results show that the THF solvent provide the better charge transfer. In a morphological view point, the phase segregation was clearly appearing by the addition of the additive on the surface of the blend films.

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.

Recent developments in biocatalysis in multiphasic ionic liquid reaction systems.

PubMed

Meyer, Lars-Erik; von Langermann, Jan; Kragl, Udo

2018-06-01

Ionic liquids are well known and frequently used 'designer solvents' for biocatalytic reactions. This review highlights recent achievements in the field of multiphasic ionic liquid-based reaction concepts. It covers classical biphasic systems including supported ionic liquid phases, thermo-regulated multi-component solvent systems (TMS) and polymerized ionic liquids. These powerful concepts combine unique reaction conditions with a high potential for future applications on a laboratory and industrial scale. The presence of a multiphasic system simplifies downstream processing due to the distribution of the catalyst and reactants in different phases.

Modeling solvent evaporation during thin film formation in phase separating polymer mixtures

DOE PAGES

Cummings, John; Lowengrub, John S.; Sumpter, Bobby G.; ...

2018-02-09

Preparation of thin films by dissolving polymers in a common solvent followed by evaporation of the solvent has become a routine processing procedure. However, modeling of thin film formation in an evaporating solvent has been challenging due to a need to simulate processes at multiple length and time scales. In this paper, we present a methodology based on the principles of linear non-equilibrium thermodynamics, which allows systematic study of various effects such as the changes in the solvent properties due to phase transformation from liquid to vapor and polymer thermodynamics resulting from such solvent transformations. The methodology allows for themore » derivation of evaporative flux and boundary conditions near each surface for simulations of systems close to the equilibrium. We apply it to study thin film microstructural evolution in phase segregating polymer blends dissolved in a common volatile solvent and deposited on a planar substrate. Finally, effects of the evaporation rates, interactions of the polymers with the underlying substrate and concentration dependent mobilities on the kinetics of thin film formation are studied.« less

Modeling solvent evaporation during thin film formation in phase separating polymer mixtures

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

Cummings, John; Lowengrub, John S.; Sumpter, Bobby G.

Preparation of thin films by dissolving polymers in a common solvent followed by evaporation of the solvent has become a routine processing procedure. However, modeling of thin film formation in an evaporating solvent has been challenging due to a need to simulate processes at multiple length and time scales. In this paper, we present a methodology based on the principles of linear non-equilibrium thermodynamics, which allows systematic study of various effects such as the changes in the solvent properties due to phase transformation from liquid to vapor and polymer thermodynamics resulting from such solvent transformations. The methodology allows for themore » derivation of evaporative flux and boundary conditions near each surface for simulations of systems close to the equilibrium. We apply it to study thin film microstructural evolution in phase segregating polymer blends dissolved in a common volatile solvent and deposited on a planar substrate. Finally, effects of the evaporation rates, interactions of the polymers with the underlying substrate and concentration dependent mobilities on the kinetics of thin film formation are studied.« less

Determination of total phthalate in cosmetics using a simple three-phase sample preparation method.

PubMed

Liu, Laping; Wang, Zhengmeng; Zhao, Sihan; Duan, Jiahui; Tao, Hu; Wang, Wenji; Liu, Shuhui

2018-02-01

A simple sample preparation method requiring minimal organic solvents is proposed for the determination of the total phthalate content in cosmetics by high-performance liquid chromatography-tandem mass spectrometry. The hydrolysis of phthalates and purification of interfering substances were performed in a three-phase system that included an upper n-hexane phase, a middle ethanol phase, and a lower aqueous alkali solution. This three-phase system utilized an incremental purification strategy. The apolar ingredients were extracted with n-hexane, the polar pigments accumulated in the ethanol phase, and the hydrolysis product, phthalic acid, remained in the hydrolysate. Under the optimized conditions, the correlation coefficients (r) for the calibration curves were 0.998-0.999 in the range 0.60-12 mol L -1 . The limit of detection was 5.1 μmol kg -1 , and the limit of quantification was 9.2 μmol kg -1 . The recoveries varied from 84 to 97% with RSDs equal to or lower than 11%. The intra-day and inter-day repeatability values, expressed as the relative standard deviation, were less than 8.7 and 9.8, respectively. No obvious matrix effect existed in the different cosmetics matrices. The validated method was applied for the analysis of 57 commercial cosmetic samples. Graphical abstract Analysis of phthalates in cosmetics using a three-phase preparation method.

Biotransformation in Double-Phase Systems: Physiological Responses of Pseudomonas putida DOT-T1E to a Double Phase Made of Aliphatic Alcohols and Biosynthesis of Substituted Catechols

PubMed Central

Rojas, Antonia; Duque, Estrella; Schmid, Andreas; Hurtado, Ana; Ramos, Juan-Luis; Segura, Ana

2004-01-01

Pseudomonas putida strain DOT-T1E is highly tolerant to organic solvents, with a logPow (the logarithm of the partition coefficient of a solvent in a two-phase water-octanol system of ≥2.5. Solvent tolerant microorganisms can be exploited to develop double-phase (organic solvent and water) biotransformation systems in which toxic substrates or products are kept in the organic phase. We tested P. putida DOT-T1E tolerance to different aliphatic alcohols with a logPow value between 2 and 4, such as decanol, nonanol, and octanol, which are potentially useful in biotransformations in double-phase systems in which compounds with a logPow around 1.5 are produced. P. putida DOT-T1E responds to aliphatic alcohols as the second phase through cis-to-trans isomerization of unsaturated cis fatty acids and through efflux of these aliphatic alcohols via a series of pumps that also extrude aromatic hydrocarbons. These defense mechanisms allow P. putida DOT-T1E to survive well in the presence of high concentrations of the aliphatic alcohols, and growth with nonanol or decanol occurred at a high rate, whereas in the presence of an octanol double-phase growth was compromised. Our results support that the logPow of aliphatic alcohols correlates with their toxic effects, as octanol (logPow = 2.9) has more negative effects in P. putida cells than 1-nonanol (logPow = 3.4) or 1-decanol (logPow = 4). A P. putida DOT-T1E derivative bearing plasmid pWW0-xylE::Km transforms m-xylene (logPow = 3.2) into 3-methylcatechol (logPow = 1.8). The amount of 3-methylcatechol produced in an aliphatic alcohol/water bioreactor was 10- to 20-fold higher than in an aqueous medium, demonstrating the usefulness of double-phase systems for this particular biotransformation. PMID:15184168

Confinement effects on lyotropic nematic liquid crystal phases of graphene oxide dispersions

NASA Astrophysics Data System (ADS)

Al-Zangana, Shakhawan; Iliut, Maria; Turner, Michael; Vijayaraghavan, Aravind; Dierking, Ingo

2017-12-01

Graphene oxide (GO) forms well ordered liquid crystal (LC) phases in polar solvents. Here, we map the lyotropic phase diagram of GO as a function of the lateral dimensions of the GO flakes, their concentration, geometrical confinement configuration and solvent polarity. GO flakes were prepared in water and transferred into other polar solvents. Polarising optical microscopy (POM) was used to determine the phase evolution through the isotropic-biphasic-nematic transitions of the GO LC. We report that the confinement volume and geometry relative to the particle size is critical for the observation of the lyotropic phase, specifically, this determines the low-end concentration limit for the detection of the GO LC. Additionally, a solvent with higher polarisability stabilises the LC phases at lower concentrations and smaller flake sizes. GO LCs have been proposed for a range of applications from display technologies to conductive fibres, and the behaviour of LC phase formation under confinement imposes a limit on miniaturisation of the dimensions of such GO LC systems which could significantly impact on their potential applications.

Development of "ultrasound-assisted dynamic extraction" and its combination with CCC and CPC for simultaneous extraction and isolation of phytochemicals.

PubMed

Zhang, Yuchi; Liu, Chunming; Li, Jing; Qi, Yanjuan; Li, Yuchun; Li, Sainan

2015-09-01

A new method for the extraction of medicinal herbs termed ultrasonic-assisted dynamic extraction (UADE) was designed and evaluated. This technique was coupled with counter-current chromatography (CCC) and centrifugal partition chromatography (CPC) and then applied to the continuous extraction and online isolation of chemical constituents from Paeonia lactiflora Pall (white peony) roots. The mechanical parameters, including the pitch and diameter of the shaft, were optimized by means of mathematical modeling. Furthermore, the configuration and mechanism of online UADE coupled with CCC and CPC were elaborated. The stationary phases of the two-phase solvent systems from CCC and CPC were utilized as the UADE solution. The extraction solution was pumped into the sample loop and then introduced into the CCC column; the target compounds were eluted with the lower aqueous phase of the two-phase solvent system. During the CCC separation, the extraction solution was continuously fed in the sample loop by turning the ten-port valve; the extraction solution was then pumped into the CPC column and eluted by the mobile phase of the two-phase solvent system mentioned above. When the first cycle of the UADE/CCC/CPC was completed, the second cycle experiment could be carried out, and so on. Four target compounds (albiflorin, benzoylpaeoniflorin, paeoniflorin, and galloylpaeoniflorin) with purities above 94.96% were successfully extracted and isolated online using the two-phase solvent system comprising ethyl acetate-n-butanol-ethanol-water (1:3.5:2:4.5, v/v/v/v). Compared with conventional extraction methods, the instrumental setup of the present method offers the advantages of automation and systematic extraction and isolation of natural products. Crown Copyright © 2015. Published by Elsevier B.V. All rights reserved.

Systematic investigations of peak deformations due to co-solvent adsorption in preparative supercritical fluid chromatography.

PubMed

Glenne, Emelie; Leek, Hanna; Klarqvist, Magnus; Samuelsson, Jörgen; Fornstedt, Torgny

2017-05-05

Strangely shaped overloaded bands were recently reported using a standard supercritical fluid chromatographic system comprising a diol column as the stationary phase and carbon dioxide with methanol as the mobile phase. Some of these overloaded elution profiles appeared strongly deformed and even had "anti-Langmuirian" shapes although their solute compounds had "Langmuirian" adsorption. To obtain a more complete understanding of the generality of these effects, the investigation was expanded to cover also other common co-solvents, such as ethanol, 2-propanol, and acetonitrile, as well as various stationary phase materials, such as silica, and 2-ethylpyridine. From this expanded study it could be confirmed that the effects of deformed overloaded solute band shapes, due to co-solvent adsorption, is general phenomena in supercritical fluid chromatographic. It could also be concluded that these effects as well as previously observed "solvent effects" or "plug effects" are entirely due to competition between the solute and solvent molecules for the adsorption sites on the stationary phase surface. Finally, guidelines were given for how to evaluate the risk of deformations occurring for a given solvent-column combination, based simply on testing retention times of solutes and co-solvent. Copyright © 2017 Elsevier B.V. All rights reserved.

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.

Size effects of solvent molecules on the phase behavior and effective interaction of colloidal systems with the bridging attraction.

PubMed

Chen, Jie; Wang, Xuewu; Kline, Steven R; Liu, Yun

2016-11-16

There has been much recent research interest towards understanding the phase behavior of colloidal systems interacting with a bridging attraction, where the small solvent particles and large solute colloidal particles can be reversibly associated with each other. These systems show interesting phase behavior compared to the more widely studied depletion attraction systems. Here, we use Baxter's two-component sticky hard sphere model with a Percus-Yevick closure to solve the Ornstein-Zernike equation and study the size effect on colloidal systems with bridging attractions. The spinodal decomposition regions, percolation transition boundaries and binodal regions are systematically investigated as a function of the relative size of the small solvent and large solute particles as well as the attraction strength between the small and large particles. In the phase space determined by the concentrations of small and large particles, the spinodal and binodal regions form isolated islands. The locations and shapes of the spinodal and binodal regions sensitively depend on the relative size of the small and large particles and the attraction strength between them. The percolation region shrinks by decreasing the size ratio, while the binodal region slightly expands with the decrease of the size ratio. Our results are very important in understanding the phase behavior for a bridging attraction colloidal system, a model system that provides insight into oppositely charged colloidal systems, protein phase behavior, and colloidal gelation mechanisms.

An Experimental and Computational Investigation into the Gas-Phase Acidities of Tyrosine and Phenylalanine: Three Structures for Deprotonated Tyrosine

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

Bokatzian, Samantha S.; Stover, Michele L.; Plummer, Chelsea E.

Using mass spectrometry and correlated molecular orbital theory, three deprotonated structures were revealed for the amino acid tyrosine. The structures were distinguished experimentally by ion/molecule reactions involving proton transfer and trimethylsilyl azide. Gas-phase acidities from proton transfer reactions and from G3(MP2) calculations generally agree well. The lowest energy structure, which was only observed experimentally using electrospray ionization from aprotic solvents, is deprotonated at the carboxylic acid group and is predicted to be highly folded. A second unfolded carboxylate structure is several kcal/mol higher in energy and primarily forms from protic solvents. Protic solvents also yield a structure deprotonated at themore » phenolic side chain, which experiments find to be intermediate in energy to the two carboxylate forms. G3(MP2) calculations indicate that the three structures differ in energy by only 2.5 kcal/mol, yet they are readily distinguished experimentally. Structural abundance ratios are dependent upon experimental conditions, including the solvent and accumulation time of ions in a hexapole. Under some conditions, carboxylate ions may convert to phenolate ions. For phenylalanine, which lacks a phenolic group, only one deprotonated structure was observed experimentally when electrosprayed from protic solvent. This agrees with G3(MP2) calculations that find the folded and unfolded carboxylate forms to differ by 0.3 kcal/mol.« less

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.

New solvent systems for gradient counter-current chromatography in separation of betanin and its derivatives from processed Beta vulgaris L. juice.

PubMed

Spórna-Kucab, Aneta; Garrard, Ian; Ignatova, Svetlana; Wybraniec, Sławomir

2015-02-06

Betalains, natural plant pigments, are beneficial compounds due to their antioxidant and possible chemoprotective properties. A mixture of betalains: betanin/isobetanin, decarboxybetanins and neobetanin from processed red beet roots (Beta vulgaris L.) juice was separated in food-grade, gradient solvent systems using high-performance counter-current chromatography (HPCCC). The decarboxylated and dehydrogenated betanins were obtained by thermal degradation of betanin/isobetanin from processed B. vulgaris L. juice under mild conditions. Two solvent systems (differing in their composition by phosphoric acid and ethanol volume gradient) consisting of BuOH-EtOH-NaClsolution-H2O-H3PO4 (v/v/v/v/v, 1300:200-1000:1300:700:2.5-10) in the 'tail-to-head' mode were run. The flow rate of the mobile phase (organic phase) was 1.0 or 2.0 ml/min and the column rotation speed was 1,600 rpm (20°C). The retention of the solvent system stationary phase (aqueous phase) was ca. 80%. The system with the acid and ethanol volume gradient consisting of BuOH-EtOH-NaClsolution-H2O-H3PO4 (v/v/v/v/v, 1300:200-240:1300:700:2.5-4.5) pumped at 2.0 ml/min was the most effective for a separation of betanin/isobetanin, 17-decarboxy-betanin/-isobetanin, 2-decarboxy-betanin/-isobetanin, 2,17-bidecarboxy-betanin/-isobetanin pairs as well as neobetanin. The pigments were detected by LC-DAD and LC-MS. The results are crucial in the application of completely food-grade solvent systems in separation of food-grade compounds as well, and the systems can possibly be extended to other ionizable and polar compounds with potential health benefits. In particular, the method is applicable for the isolation and purification of betalains present in such rich sources as B. vulgaris L. roots as well as cacti fruits and Amaranthaceae flowering plants due to modification possibilities of the solvent systems polarity. Copyright © 2014 Elsevier B.V. All rights reserved.

Peculiarity of two thermodynamically-stable morphologies and their impact on the efficiency of small molecule bulk heterojunction solar cells

DOE PAGES

Herath, Nuradhika; Das, Sanjib; Keum, Jong K.; ...

2015-08-28

Structural characteristics of the active layers in organic photovoltaic (OPV) devices play a critical role in charge generation, separation and transport. Here we report on morphology and structural control of p-DTS(FBTTh 2) 2:PC 71BM films by means of thermal annealing and 1,8-diiodooctane (DIO) solvent additive processing, and correlate it to the device performance. By combining surface imaging with nanoscale depth-sensitive neutron reflectometry (NR) and X-ray diffraction, three-dimensional morphologies of the films are reconstituted with information extending length scales from nanometers to microns. DIO promotes the formation of a well-mixed donor-acceptor vertical phase morphology with a large population of small p-DTS(FBTTh2)2more » nanocrystals arranged in an elongated domain network of the film, thereby enhancing the device performance. In contrast, films without DIO exhibit three-sublayer vertical phase morphology with phase separation in agglomerated domains. Our findings are supported by thermodynamic description based on the Flory-Huggins theory with quantitative evaluation of pairwise interaction parameters that explain the morphological changes resulting from thermal and solvent treatments. Our study reveals that vertical phase morphology of small-molecule based OPVs is significantly different from polymer-based systems. Lastly, the significant enhancement of morphology and information obtained from theoretical modeling may aid in developing an optimized morphology to enhance device performance for OPVs.« less

A green ultrasonic-assisted liquid-liquid microextraction based on deep eutectic solvent for the HPLC-UV determination of ferulic, caffeic and cinnamic acid from olive, almond, sesame and cinnamon oil.

PubMed

Khezeli, Tahere; Daneshfar, Ali; Sahraei, Reza

2016-04-01

A simple, inexpensive and sensitive ultrasonic-assisted liquid-liquid microextraction method based on deep eutectic solvent (UALLME-DES) was used for the extraction of three phenolic acids (ferulic, caffeic and cinnamic) from vegetable oils. In a typical experiment, deep eutectic solvent as green extraction solvent was added to n-hexane (as a typical oil medium) containing target analytes. Subsequently, the extraction was accelerated by sonication. After the extraction, phase separation (DES rich phase/n-hexane phase) was performed by centrifugation. DES rich phase (lower phase) was withdrawn by a micro-syringe and submitted to isocratic reverse-phase HPLC with UV detection. Under optimum conditions obtained by response surface methodology (RSM) and desirability function (DF), the method has good linear calibration ranges (between 1.30 and 1000 µg L(-1)), coefficients of determination (r(2)>0.9949) and low limits of detection (between 0.39 and 0.63 µg L(-1)). This procedure was successfully applied to the determination of target analytes in olive, almond, sesame and cinnamon oil samples. The relative mean recoveries ranged from 94.7% to 104.6%. Copyright © 2015 Elsevier B.V. All rights reserved.

Simultaneous phase and morphology controllable synthesis of copper selenide films by microwave-assisted nonaqueous approach

NASA Astrophysics Data System (ADS)

Li, Jing; Fa, Wenjun; Li, Yasi; Zhao, Hongxiao; Gao, Yuanhao; Zheng, Zhi

2013-02-01

Copper selenide films with different phase and morphology were synthesized on copper substrate through controlling reaction solvent by microwave-assisted nonaqueous approach. The films were characterized by X-ray diffraction (XRD) and scanning electron microscope (SEM). The result showed that the pure films could be obtained using cyclohexyl alcohol or benzyl alcohol as solvent. The cubic Cu2-xSe dendrites were synthesized in cyclohexyl alcohol reaction system and hexagonal CuSe flaky crystals were obtained with benzyl alcohol as solvent.

Interdroplet attractive forces in AOT water-in-oil microemulsions formed in subcritical and supercritical solvents

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

Tingey, J.M.; Fulton, J.L.; Smith, R.D.

1990-03-08

The van der Waals attractive interactions between aqueous droplets in water-in-oil type microemulsions have been investigated for a range of continuous-phase solvents including the alkanes from methane to isooctane and the noble gases, krypton and xenon. Hamaker constants for water droplets with surfactant shells of the sodium bis(2-ethylhexyl) sulfosuccinate (AOT) in subcritical and supercritical solvents were calculated by using Lifshitz theory and the resulting interaction potential calculations qualitatively account for many features of the phase behavior of these systems.

Aqueous biphasic systems formed by deep eutectic solvent and new-type salts for the high-performance extraction of pigments.

PubMed

Zhang, Hongmei; Wang, Yuzhi; Zhou, Yigang; Chen, Jing; Wei, Xiaoxiao; Xu, Panli

2018-05-01

Deep eutectic solvent (DES) composed of polypropylene glycol 400 (PPG 400) and tetrabutylammonium bromide (TBAB) was combined with a series of new-type salts such as quaternary ammonium salts, amino acid and polyols to form Aqueous Biphasic Systems (ABSs). Phase-forming ability of the salts was investigated firstly. The results showed that polyols had a relatively weak power to produce phases within studied scopes. And the shorter of carbon chain length of salts, the easier to obtain phase-splitting. Then partitioning of three pigments in PPG 400/betaine-based ABSs was addressed to investigate the effect of pigments' hydrophobicity on extraction efficiency. It was found that an increase in hydrophobicity contributed to the migration of pigments in the DES-rich phase. On the other hand, with a decline in phase-forming ability of salts, the extraction efficiency of the whole systems started to go down gradually. Based on the results, selective separation experiment was conducted successfully in the PPG 400/betaine-based systems, including more than 93.00% Sudan Ⅲ in the top phase and about 80.00% sunset yellow FCF/amaranth in the bottom phase. Additionally, ABSs constructed by DES/betaine for partitioning amaranth were further utilized to explore the performances of influence factors and back extraction. It can be concluded that after the optimization above 98.00% amaranth was transferred into the top phase. And 67.98% amaranth can be transferred into the bottom phase in back-extraction experiment. At last, dynamic light scattering (DLS) and transmission electron microscope (TEM) were applied to probe into extraction mechanism. The results demonstrated that hydrophobicity played an important role in the separation process of pigments. Through combining with new-type DES, this work was devoted to introducing plentiful salts as novel compositions of ABSs and providing an eco-friendly extraction way for partitioning pigments, which boosted development of ABSs in the monitoring food safety field. Copyright © 2018 Elsevier B.V. All rights reserved.

Developments toward large-scale bacterial bioprocesses in the presence of bulk amounts of organic solvents.

PubMed

Schmid, A; Kollmer, A; Mathys, R G; Witholt, B

1998-08-01

Many pseudomonads and other bacteria can grow on aliphatic and aromatic hydrocarbons that occur in the environment. We are examining the potential of such organisms as biocatalysts for the oxidation of a variety of substituted aliphatic and aromatic compounds. To attain a high production rate of oxidation products via such biotransformations, we have focused on two-liquid phase culture systems. In these systems, cells are grown in liquid media consisting of an aqueous phase containing water-soluble growth substrates and droplets of a water-immicible organic solvent containing bioconversion substrates and products. For industrial applications of such two-liquid phase processes, several questions remain. What are the maximum rates at which apolar compounds can be transferred from the apolar phase to cells growing in the aqueous phase, i.e., what are the maximum space-time yields attainable in two-liquid phase fermentations under practical conditions? What does an efficient downstream processing of two-liquid phase medium involve? What safety regimes should be considered in working with flammable organic solvents? Can elevated pressure be used to increase oxygen transfer? Based on answers to these questions, we have recently developed a high-pressure, explosion-proof bioreactor system with Bioengineering AG (Wald, Switzerland), which will be installed in our pilot plant and used to explore two-liquid phase bioconversions at a pilot scale.

Supramolecular Complexes Formed by the Self-assembly of Hydrophobic Bis(Zn(2+)-cyclen) Complexes, Copper, and Di- or Triimide Units for the Hydrolysis of Phosphate Mono- and Diesters in Two-Phase Solvent Systems (Cyclen=1,4,7,10-Tetraazacyclododecane).

PubMed

Hisamatsu, Yosuke; Miyazawa, Yuya; Yoneda, Kakeru; Miyauchi, Miki; Zulkefeli, Mohd; Aoki, Shin

2016-01-01

We previously reported on supramolecular complexes 4 and 5, formed by the 4 : 4 : 4 or 2 : 2 : 2 assembly of a dimeric zinc(II) complex (Zn2L(1)) having 2,2'-bipyridyl linker, dianion of cyanuric acid (CA) or 5,5-diethylbarbituric acid (Bar), and copper(II) ion (Cu(2+)) in an aqueous solution. The supermolecule 4 possesses Cu2(μ-OH)2 centers and catalyzes hydrolysis of phosphate monoester dianion, mono(4-nitrophenyl)phosphate (MNP), at neutral pH. In this manuscript, we report on design and synthesis of hydrophobic supermolecules 9 and 10 by 4 : 4 : 4 and 2 : 2 : 2 self-assembly of hydrophobic Zn2L(2) and Zn2L(3) containing long alkyl chains, CA or Bar, and Cu(2+) and their phosphatase activity for the hydrolysis of MNP and bis(4-nitrophenyl)phosphate (BNP) in two-phase solvent systems. We assumed that the Cu2(μ-OH)2 active sites of 9 and 10 would be more stable in organic solvent than in aqueous solution and that product inhibition of the supermolecules might be avoided by the release of HPO4(2-) into the aqueous layer. The findings indicate that 9 and 10 exhibit phosphatase activity in the two-phase solvent system, although catalytic turnover was not observed. Furthermore, the hydrolysis of BNP catalyzed by the hydrophobic 2 : 2 : 2 supermolecules in the two-phase solvent system is described.

Preparative separation and identification of novel subsidiary colors of the color additive D&C Red No. 33 (Acid Red 33) using spiral high-speed counter-current chromatography☆

PubMed Central

Weisz, Adrian; Ridge, Clark D.; Mazzola, Eugene P.; Ito, Yoichiro

2015-01-01

Three low-level subsidiary color impurities (A, B, and C) often present in batches of the color additive D&C Red No. 33 (R33, Acid Red 33, Colour Index No. 17200) were separated from a portion of R33 by spiral high-speed counter-current chromatography (HSCCC). The separation involved use of a very polar solvent system, 1-BuOH/5 mM aq. (NH4)2SO4. Addition of ammonium sulfate to the lower phase forced partition of the components into the upper phase, thereby eliminating the need to add a hydrophobic counterion as was previously required for separations of components from sulfonated dyes. The very polar solvent system used would not have been retained in a conventional multi-layer coil HSCCC instrument, but the spiral configuration enabled retention of the stationary phase, and thus, the separation was possible. A 1 g portion of R33 enriched in A, B, and C was separated using the upper phase of the solvent system as the mobile phase. The retention of the stationary phase was 38.1%, and the separation resulted in 4.8 mg of A of >90% purity, 18.3 mg of B of >85% purity, and 91 mg of C of 65–72% purity. A second separation of a portion of the C mixture resulted in 7 mg of C of >94% purity. The separated impurities were identified by high-resolution mass spectrometry and NMR spectroscopic techniques as follows: 5-amino-3-biphenyl-3-ylazo-4-hydroxy-naphthalene-2,7-disulfonic acid, A; 5-amino-4-hydroxy-6-phenyl-3-phenylazo-naphthalene-2,7-disulfonic acid, B; and 5-amino-4-hydroxy-3,6-bis-phenylazo-naphthalene-2,7-disulfonic acid, C. The isomers A and B are compounds reported for the first time. Application of the spiral HSCCC method resulted in the additional benefit of yielding 930 mg of the main component of R33, 5-amino-4-hydroxy-3-phenylazo-naphthalene-2,7-disulfonic acid, of >97% purity. PMID:25591404

Preparative separation and identification of novel subsidiary colors of the color additive D&C Red No. 33 (Acid Red 33) using spiral high-speed counter-current chromatography.

PubMed

Weisz, Adrian; Ridge, Clark D; Mazzola, Eugene P; Ito, Yoichiro

2015-02-06

Three low-level subsidiary color impurities (A, B, and C) often present in batches of the color additive D&C Red No. 33 (R33, Acid Red 33, Colour Index No. 17200) were separated from a portion of R33 by spiral high-speed counter-current chromatography (HSCCC). The separation involved use of a very polar solvent system, 1-BuOH/5mM aq. (NH4)2SO4. Addition of ammonium sulfate to the lower phase forced partition of the components into the upper phase, thereby eliminating the need to add a hydrophobic counterion as was previously required for separations of components from sulfonated dyes. The very polar solvent system used would not have been retained in a conventional multi-layer coil HSCCC instrument, but the spiral configuration enabled retention of the stationary phase, and thus, the separation was possible. A 1g portion of R33 enriched in A, B, and C was separated using the upper phase of the solvent system as the mobile phase. The retention of the stationary phase was 38.1%, and the separation resulted in 4.8 mg of A of >90% purity, 18.3mg of B of >85% purity, and 91 mg of C of 65-72% purity. A second separation of a portion of the C mixture resulted in 7 mg of C of >94% purity. The separated impurities were identified by high-resolution mass spectrometry and NMR spectroscopic techniques as follows: 5-amino-3-biphenyl-3-ylazo-4-hydroxy-naphthalene-2,7-disulfonic acid, A; 5-amino-4-hydroxy-6-phenyl-3-phenylazo-naphthalene-2,7-disulfonic acid, B; and 5-amino-4-hydroxy-3,6-bis-phenylazo-naphthalene-2,7-disulfonic acid, C. The isomers A and B are compounds reported for the first time. Application of the spiral HSCCC method resulted in the additional benefit of yielding 930 mg of the main component of R33, 5-amino-4-hydroxy-3-phenylazo-naphthalene-2,7-disulfonic acid, of >97% purity. Published by Elsevier B.V.

Structural and phase transitions of one and two polymer mushrooms in poor solvent

NASA Astrophysics Data System (ADS)

Yang, Delian; Wang, Qiang

2014-05-01

Using the recently proposed fast lattice Monte Carlo (FLMC) simulations and the corresponding lattice self-consistent field (LSCF) calculations based on the same model system, where multiple occupancy of lattice sites is allowed [Q. Wang, Soft Matter 5, 4564 (2009); Q. Wang, Soft Matter 5, 6206 (2010)], we studied the coil-globule transition (CGT) of one-mushroom systems and the fused-separated transition (FST) of two-mushroom systems, where a polymer mushroom is formed by a group of n homopolymer chains each of N segments end-grafted at the same point onto a flat substrate and immersed in a poor solvent. With our soft potential that allows complete particle overlapping, LSCF theory neglecting the system fluctuations/correlations becomes exact in the limit of n → ∞, and FLMC results approach LSCF predictions with increasing n. Using LSCF calculations, we systematically constructed the phase diagrams of one- and two-mushroom systems. A second-order symmetric-asymmetric transition (SAT) was found in the globule state of one-mushroom systems, where the rotational symmetry around the substrate normal passing through the grafting point is broken in each individual configuration but preserved by the degeneracy of different orientations of these asymmetric configurations. Three different states were also found in two-mushroom systems: separated coils, separated globules, and fused globule. We further studied the coupling between FST in two-mushroom systems and CGT and SAT of each mushroom. Finally, direct comparisons between our simulation and theoretical results, without any parameter-fitting, unambiguously and quantitatively revealed the fluctuation/correlation effects on these phase transitions.

An assessment of alternatives for replacing Freon 113 in bench type electrical circuit board cleaning at Fermi National Accelerator Laboratory

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

Isakson, K.; Vessell, A.L.

1994-07-01

Fermilab is presently phasing out all solvents containing Freon-113 (CFC-113) as part of the continuing Waste Minimization Program. These solvents are used primarily in cleaning the flux off of electronic circuit boards after soldering, specifically in bench type work. Title VI of the Clean Air Act mandates a production phase-out for ozone depleting substances, like CFC-113, by the year 2000. Our study addresses this issue by evaluating and choosing alternative non-CFC solvents to replace the CFC-1 13 solvents at Fermilab. Several potential non-CFC cleaning solvents were tested. The evaluation took place in three parts: controlled experimental evaluation, chemical composition evaluation,more » and employee performed evaluation. First, we performed a controlled nine-step procedure with the potential solvents where each was evaluated in categories such as cleaning effectiveness, odor, residue, type of output and drying time. Next, we listed the chemical composition of each solvent. We noted which solvents contained hydrochlorofluorocarbons because they are targeted for phase-out in the future and will be recognized as interim solutions only. Finally, after preliminary testing, five solvents were chosen as the best options. These solvents were sent to be tested by Fermilab employees who use such materials. Their opinions are valuable not only because they are knowledgeable in this field, but also because they will be using the solvents chosen to replace the CFC-113 solvents. The results favored two ``best alternatives``: Safezone Solvent Flux Remover by Miller-Stephenson and E-Series CFC Free Flux-Off 2000 by Chemtech. Another possible solution also pursued is the no-clean solder option. In our study, we were not able to thoroughly investigate the many types of no-clean solders because of time and financial constraints. The testing that was done, however, showed that no-clean solder was a viable alternative in many cases.« less

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.

Phase Equilibria and Ionic Solvation in the Lithium Tetrafluoroborate-Dimethylsulfoxide System

NASA Astrophysics Data System (ADS)

Gafurov, M. M.; Kirillov, S. A.; Gorobets, M. I.; Rabadanov, K. Sh.; Ataev, M. B.; Tretyakov, D. O.; Aydemirov, K. M.

2015-01-01

The phase diagram and electrical conductivity isotherms for the lithium tetrafluoroborate (LiBF4)-dimethylsulfoxide (DMSO) system and Raman spectra of DMSO and the LiBF4-DMSO solution were studied. Spectroscopic signatures of a H-bond between DMSO and BF4 - ions were found. The bonds of Li+ ions to the solvent were stronger than the bonds in DMSO dimers because formation of the solvate destroyed dimeric DMSO molecules. The τω values for DMSO molecules in the Li+-ion solvate shell of the LiBF4-DMSO system were similar to those for associated solvent molecules.

Preparative separation of six rhynchophylla alkaloids from Uncaria macrophylla wall by pH-zone refining counter-current chromatography.

PubMed

Zhang, Qinghai; Lin, Changhu; Duan, Wenjuan; Wang, Xiao; Luo, Aiqin

2013-12-12

pH-Zone refining counter-current chromatography was successfully applied to the preparative isolation and purification of six alkaloids from the ethanol extracts of Uncaria macrophylla Wall. Because of the low content of alkaloids (about 0.2%, w/w) in U. macrophylla Wall, the target compounds were enriched by pH-zone refining counter-current chromatography using a two-phase solvent system composed of petroleum ether-ethyl acetate-isopropanol-water (2:6:3:9, v/v), adding 10 mM triethylamine in organic stationary phase and 5 mM hydrochloric acid in aqueous mobile phase. Then pH-zone refining counter-current chromatography using the other two-phase solvent system was used for final purification. Six target compounds were finally isolated and purified by following two-phase solvent system composed of methyl tert-butyl ether (MTBE)-acetonitrile-water (4:0.5:5, v/v), adding triethylamine (TEA) (10 mM) to the organic phase and HCl (5 mM) to aqueous mobile phase. The separation of 2.8 g enriched total alkaloids yielded 36 mg hirsutine, 48 mg hirsuteine, 82 mg uncarine C, 73 mg uncarine E, 163 mg rhynchophylline, and 149 mg corynoxeine, all with purities above 96% as verified by HPLC Their structures were identified by electrospray ionization-mass spectrometry (ESI-MS) and 1H-NMR spectroscopy.

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

PubMed

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

2004-02-06

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

Self-association of short-chain nonionic amphiphiles in binary and ternary systems: comparison between the cleavable ethylene glycol monobutyrate and its ether counterparts.

PubMed

Zhu, Ying; Fournial, Anne-Gaëlle; Molinier, Valérie; Azaroual, Nathalie; Vermeersch, Gaston; Aubry, Jean-Marie

2009-01-20

In the context of environmental concerns for the production of surface active species, the introduction of a carbonyl function into the skeleton of ethyleneglycol-derived solvo-surfactants is a way to access cleavable compounds with presumed enhanced biodegradability. Ethylene glycol monobutyrate (C(3)COE(1)) was synthesized and compared to its ether counterparts, ethylene glycol monopropyl (C(3)E(1)) and monobutyl ethers (C(4)E(1)), to assess the effect of the insertion of a carbonyl function in the skeleton of short-chain ethoxylated amphiphilic compounds. In aqueous solutions, the ester has intermediate behavior between that of the two ethers with regard to surface tension, solubilization of Me-naphtalene in water, and self-diffusion by PGSE NMR. In ternary systems, C(3)COE(1) and C(3)E(1) have the same optimal oil (EACN = 2.8), which is much more polar than that of C(4)E(1) (EACN = 8.5). With regard to the ability to form structured systems, the behavior in water does not differ significantly for the three compounds, and the transition between nonassociating solvents and amphiphilic solvents, sometimes called solvo-surfactants, is gradual. In ternary systems, however, only C(4)E(1) and C(3)COE(1) form a third phase near the optimal formulation, which tends to show that C(3)COE(1) possesses the minimum amphiphilicity to get a structuration. Self-diffusion NMR studies of the one-phase domains do not, however, allow us to distinguish between different degrees of organization in the three systems.

Studies on a new class of organogelator containing 2-anthracenecarboxylic acid: influence of gelator and solvent on stereochemistry of the photodimers.

PubMed

Dawn, Arnab; Fujita, Norifumi; Haraguchi, Shuichi; Sada, Kazuki; Tamaru, Shun-ichi; Shinkai, Seiji

2009-11-07

A new class of binary organogelator (G1, G2 and G3) based on 2-anthracenecarboxylic acid (2Ac), attached noncovalently with the gelator counterpart containing a 3,4,5-tris(n-dodecyloxy)benzoylamide backbone has been developed. Among the three gelators, two (G2 and G3) are chiral containing D-alanine or L-2-phenylglycine moieties, respectively. They can act as efficient gelators of organic solvents with varying polarity depending upon the gelator systems. Gelator G1 even gelates chiral solvents. The photoirradiation of the gel samples produces photocyclodimers having different degrees of stereoselectivity for different systems. Gels with G1 and G2 produce head-to-head (h-h) photodimers as major products, whereas the stereoselectivity is reversed for the gels with G3 producing head-to-tail (h-t) photodimers as major products. Among those, G2/cyclohexane gel shows the highest degree of stereoselectivity, producing only h-h photodimers with some significant amount of chiral induction. Other chiral systems exhibit low to moderate chiral inductions. The gelator G1 can differentiate between the racemic and enantiomerically pure varieties of a solvent by exhibiting different gel melting temperatures (T(gel)). For different gel systems, T(gel) increases in all the cases as a consequence of photoreaction, except for the G2/cyclohexane gel, where a prominent gel-to-sol phase transition can be observed during the photoreaction. Hydrogen-bonding and pi-pi stacking interactions play the principal roles in constructing the gel structure. The morphologies of the gel systems vary between one-dimensional fibrils and a fibrillar network structure. In addition, the influences of the gelator and solvent polarity on the rate of photoreactions, photoproduct distributions as well as gel structures are investigated.

Si-Ge-metal ternary phase diagram calculations

NASA Technical Reports Server (NTRS)

Fleurial, J. P.; Borshchevsky, A.

1990-01-01

Solution crystal growth and doping conditions of Si-Ge alloys used for high-temperature thermoelectric generation are determined here. Liquid-phase epitaxy (LPE) has been successfully employed recently to obtain single-crystalline homogeneous layers of Si-Ge solid solutions from a liquid metal solvent. Knowledge of Si-Ge-metallic solvent ternary phase diagrams is essential for further single-crystal growth development. Consequently, a thermodynamic equilibrium model was used to calculate the phase diagrams of the Si-Ge-M systems, including solid solubilities, where M is Al, Ga, In, Sn, Pb, Sb, or Bi. Good agreement between calculated liquidus and solidus data and experimental DTA and microprobe results was obtained. The results are used to compare the suitability of the different systems for crystal growth (by LPE-type process).

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

Surface radical chain-transfer reaction in deep eutectic solvents for preparation of silica-grafted stationary phases in hydrophilic interaction chromatography.

PubMed

Yang, Beibei; Cai, Tianpei; Li, Zhan; Guan, Ming; Qiu, Hongdeng

2017-12-01

In this paper, deep eutectic solvents (DESs) were firstly used as new and green solvents for the preparation of polymer-grafted silica stationary phases. 1-Vinylimidazole and acrylic acid were homopolymerized and copolymerized on silica via surface radical chain-transfer reaction in the DESs. Three stationary phases including poly(1-vinylimidazole)-, poly(acrylic acid)-, poly(1-vinylimidazole-co-acrylic acid)-grafted silica were obtained and characterized by elemental analysis and Fourier transform infrared spectroscopy. Their hydrophilic interaction chromatographic properties were investigated for separation of nucleosides, nucleobases, saccharides and amino acids. The retention changes of nucleosides and nucleobases on these columns were investigated under different chromatographic conditions including acetonitrile content, salt concentration, pH of mobile phase and column temperature. The repeatability of these columns was also investigated. The results demonstrate that DESs can be used as new media for the synthesis of silica-based stationary phases by homopolymerization and copolymerization on the surface of porous silica particles. Copyright © 2017 Elsevier B.V. All rights reserved.

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

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

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

2012-08-03

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

Natural deep eutectic solvents as the major mobile phase components in high-performance liquid chromatography-searching for alternatives to organic solvents.

PubMed

Sutton, Adam T; Fraige, Karina; Leme, Gabriel Mazzi; da Silva Bolzani, Vanderlan; Hilder, Emily F; Cavalheiro, Alberto J; Arrua, R Dario; Funari, Cristiano Soleo

2018-06-01

Over the past six decades, acetonitrile (ACN) has been the most employed organic modifier in reversed-phase high-performance liquid chromatography (RP-HPLC), followed by methanol (MeOH). However, from the growing environmental awareness that leads to the emergence of "green analytical chemistry," new research has emerged that includes finding replacements to problematic ACN because of its low sustainability. Deep eutectic solvents (DES) can be produced from an almost infinite possible combinations of compounds, while being a "greener" alternative to organic solvents in HPLC, especially those prepared from natural compounds called natural DES (NADES). In this work, the use of three NADES as the main organic component in RP-HPLC, rather than simply an additive, was explored and compared to the common organic solvents ACN and MeOH but additionally to the greener ethanol for separating two different mixtures of compounds, one demonstrating the elution of compounds with increasing hydrophobicity and the other comparing molecules of different functionality and molar mass. To utilize NADES as an organic modifier and overcome their high viscosity monolithic columns, temperatures at 50 °C and 5% ethanol in the mobile phase were used. NADES are shown to give chromatographic performances in between those observed for ACN and MeOH when eluotropic strength, resolution, and peak capacity were taken into consideration, while being less environmentally impactful as shown by the HPLC-Environmental Assessment Tool (HPLC-EAT) metric. With the development of proper technologies, DES could open a new class of mobile phases increasing the possibilities of new separation selectivities while reducing the environmental impact of HPLC analyses. Graphical abstract Natural deep eutectic solvents versus traditional solvents in HPLC.

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.

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

PubMed

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

2018-05-14

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

A self-consistent phase-field approach to implicit solvation of charged molecules with Poisson-Boltzmann electrostatics

NASA Astrophysics Data System (ADS)

Sun, Hui; Wen, Jiayi; Zhao, Yanxiang; Li, Bo; McCammon, J. Andrew

2015-12-01

Dielectric boundary based implicit-solvent models provide efficient descriptions of coarse-grained effects, particularly the electrostatic effect, of aqueous solvent. Recent years have seen the initial success of a new such model, variational implicit-solvent model (VISM) [Dzubiella, Swanson, and McCammon Phys. Rev. Lett. 96, 087802 (2006) and J. Chem. Phys. 124, 084905 (2006)], in capturing multiple dry and wet hydration states, describing the subtle electrostatic effect in hydrophobic interactions, and providing qualitatively good estimates of solvation free energies. Here, we develop a phase-field VISM to the solvation of charged molecules in aqueous solvent to include more flexibility. In this approach, a stable equilibrium molecular system is described by a phase field that takes one constant value in the solute region and a different constant value in the solvent region, and smoothly changes its value on a thin transition layer representing a smeared solute-solvent interface or dielectric boundary. Such a phase field minimizes an effective solvation free-energy functional that consists of the solute-solvent interfacial energy, solute-solvent van der Waals interaction energy, and electrostatic free energy described by the Poisson-Boltzmann theory. We apply our model and methods to the solvation of single ions, two parallel plates, and protein complexes BphC and p53/MDM2 to demonstrate the capability and efficiency of our approach at different levels. With a diffuse dielectric boundary, our new approach can describe the dielectric asymmetry in the solute-solvent interfacial region. Our theory is developed based on rigorous mathematical studies and is also connected to the Lum-Chandler-Weeks theory (1999). We discuss these connections and possible extensions of our theory and methods.

A self-consistent phase-field approach to implicit solvation of charged molecules with Poisson-Boltzmann electrostatics.

PubMed

Sun, Hui; Wen, Jiayi; Zhao, Yanxiang; Li, Bo; McCammon, J Andrew

2015-12-28

Dielectric boundary based implicit-solvent models provide efficient descriptions of coarse-grained effects, particularly the electrostatic effect, of aqueous solvent. Recent years have seen the initial success of a new such model, variational implicit-solvent model (VISM) [Dzubiella, Swanson, and McCammon Phys. Rev. Lett. 96, 087802 (2006) and J. Chem. Phys. 124, 084905 (2006)], in capturing multiple dry and wet hydration states, describing the subtle electrostatic effect in hydrophobic interactions, and providing qualitatively good estimates of solvation free energies. Here, we develop a phase-field VISM to the solvation of charged molecules in aqueous solvent to include more flexibility. In this approach, a stable equilibrium molecular system is described by a phase field that takes one constant value in the solute region and a different constant value in the solvent region, and smoothly changes its value on a thin transition layer representing a smeared solute-solvent interface or dielectric boundary. Such a phase field minimizes an effective solvation free-energy functional that consists of the solute-solvent interfacial energy, solute-solvent van der Waals interaction energy, and electrostatic free energy described by the Poisson-Boltzmann theory. We apply our model and methods to the solvation of single ions, two parallel plates, and protein complexes BphC and p53/MDM2 to demonstrate the capability and efficiency of our approach at different levels. With a diffuse dielectric boundary, our new approach can describe the dielectric asymmetry in the solute-solvent interfacial region. Our theory is developed based on rigorous mathematical studies and is also connected to the Lum-Chandler-Weeks theory (1999). We discuss these connections and possible extensions of our theory and methods.

A self-consistent phase-field approach to implicit solvation of charged molecules with Poisson–Boltzmann electrostatics

PubMed Central

Sun, Hui; Wen, Jiayi; Zhao, Yanxiang; Li, Bo; McCammon, J. Andrew

2015-01-01

Dielectric boundary based implicit-solvent models provide efficient descriptions of coarse-grained effects, particularly the electrostatic effect, of aqueous solvent. Recent years have seen the initial success of a new such model, variational implicit-solvent model (VISM) [Dzubiella, Swanson, and McCammon Phys. Rev. Lett. 96, 087802 (2006) and J. Chem. Phys. 124, 084905 (2006)], in capturing multiple dry and wet hydration states, describing the subtle electrostatic effect in hydrophobic interactions, and providing qualitatively good estimates of solvation free energies. Here, we develop a phase-field VISM to the solvation of charged molecules in aqueous solvent to include more flexibility. In this approach, a stable equilibrium molecular system is described by a phase field that takes one constant value in the solute region and a different constant value in the solvent region, and smoothly changes its value on a thin transition layer representing a smeared solute-solvent interface or dielectric boundary. Such a phase field minimizes an effective solvation free-energy functional that consists of the solute-solvent interfacial energy, solute-solvent van der Waals interaction energy, and electrostatic free energy described by the Poisson–Boltzmann theory. We apply our model and methods to the solvation of single ions, two parallel plates, and protein complexes BphC and p53/MDM2 to demonstrate the capability and efficiency of our approach at different levels. With a diffuse dielectric boundary, our new approach can describe the dielectric asymmetry in the solute-solvent interfacial region. Our theory is developed based on rigorous mathematical studies and is also connected to the Lum–Chandler–Weeks theory (1999). We discuss these connections and possible extensions of our theory and methods. PMID:26723595

Surface area generation and droplet size control in solvent extraction systems utilizing high intensity electric fields

DOEpatents

Scott, Timothy C.; Wham, Robert M.

1988-01-01

A method and system for solvent extraction where droplets are shattered by a high intensity electric field. These shattered droplets form a plurality of smaller droplets which have a greater combined surface area than the original droplet. Dispersion, coalescence and phase separation are accomplished in one vessel through the use of the single pulsing high intensity electric field. Electric field conditions are chosen so that simultaneous dispersion and coalescence are taking place in the emulsion formed in the electric field. The electric field creates a large amount of interfacial surface area for solvent extraction when the droplet is disintegrated and is capable of controlling droplet size and thus droplet stability. These operations take place in the presence of a counter current flow of the continuous phase.

Constitutive equations for an electroactive polymer

NASA Astrophysics Data System (ADS)

Tixier, Mireille; Pouget, Joël

2016-07-01

Ionic electroactive polymers can be used as sensors or actuators. For this purpose, a thin film of polyelectrolyte is saturated with a solvent and sandwiched between two platinum electrodes. The solvent causes a complete dissociation of the polymer and the release of small cations. The application of an electric field across the thickness results in the bending of the strip and vice versa. The material is modeled by a two-phase continuous medium. The solid phase, constituted by the polymer backbone inlaid with anions, is depicted as a deformable porous media. The liquid phase is composed of the free cations and the solvent (usually water). We used a coarse grain model. The conservation laws of this system have been established in a previous work. The entropy balance law and the thermodynamic relations are first written for each phase and then for the complete material using a statistical average technique and the material derivative concept. One deduces the entropy production. Identifying generalized forces and fluxes provides the constitutive equations of the whole system: the stress-strain relations which satisfy a Kelvin-Voigt model, generalized Fourier's and Darcy's laws and the Nernst-Planck equation.

Protein separation through preliminary experiments concerning pH and salt concentration by tube radial distribution chromatography based on phase separation multiphase flow using a polytetrafluoroethylene capillary tube.

PubMed

Kan, Hyo; Tsukagoshi, Kazuhiko

2017-07-01

Protein mixtures were separated using tube radial distribution chromatography (TRDC) in a polytetrafluoroethylene (PTFE) capillary (internal diameter=100µm) separation tube. Separation by TRDC is based on the annular flow in phase separation multiphase flow and features an open-tube capillary without the use of specific packing agents or application of high voltages. Preliminary experiments were conducted to examine the effects of pH and salt concentration on the phase diagram of the ternary mixed solvent solution of water-acetonitrile-ethyl acetate (8:2:1 volume ratio) and on the TRDC system using the ternary mixed solvent solution. A model protein mixture containing peroxidase, lysozyme, and bovine serum albumin was analyzed via TRDC with the ternary mixed solvent solution at various pH values, i.e., buffer-acetonitrile-ethyl acetate (8:2:1 volume ratio). Protein was separated on the chromatograms by the TRDC system, where the elution order was determined by the relation between the isoelectric points of protein and the pH values of the solvent solution. Copyright © 2017 Elsevier B.V. All rights reserved.

Application of non-ionic surfactant as a developed method for the enhancement of two-phase solvent bar microextraction for the simultaneous determination of three phthalate esters from water samples.

PubMed

Bandforuzi, Samereh Ranjbar; Hadjmohammadi, Mohammad Reza

2018-08-03

The extraction of phthalate esters (PEs) from aqueous matrices using two-phase solvent bar microextraction by organic micellar phase was investigated. A short hollow fiber immobilized with reverse micelles of Brij 35 surfactant in 1-octanol was served as the solvent bar for microextraction. Experimental results show that the extraction efficiency were much higher using two-phase solvent bar microextraction based on non-ionic surfactant than conventional two-phase solvent bar microextraction because of a positive effect of surfactant-containing extraction phase in promoting the partition process by non-ionic intermolecular forces such as polar and hydrophobicity interactions. The nature of the extraction solvent, type and concentration of non-ionic surfactant, extraction time, sample pH, temperature, stirring rate and ionic strength were the effecting parameters which optimized to obtain the highest extraction recovery. Analysis of recovered analytes was carried out with high performance liquid chromatography coupled with ultraviolet detection (HPLC-UV). Under the optimum conditions, linearity was observed in the range of 1-800 ng mL -1 for dimethylphthalate (DMP) and 0.5-800 ng mL -1 for diethylphthalate (DEP) and di-n-butyl phthalate (DBP) with correlation determination values above 0.99 for them. The limits of detection and quantification were ranged from 0.012 to 0.03 ng mL -1 and 0.04-0.1 ng mL -1 , respectively. The ranges of intra-day and inter-day RSD (n = 3) at 20 ng mL -1 of PEs were 1.8-2.1% and 2.1-2.6%, respectively. Results showed that developed method can be a very powerful, innovative and promising sample preparation technique in PEs analysis from environmental and drinking water samples. Copyright © 2018. Published by Elsevier B.V.

Solvent induced rapid modulation of micro/nano structures of metal carboxylates coordination polymers: mechanism and morphology dependent magnetism.

PubMed

Liu, Kun; Shen, Zhu-Rui; Li, Yue; Han, Song-De; Hu, Tong-Liang; Zhang, Da-Shuai; Bu, Xian-He; Ruan, Wen-Juan

2014-08-12

Rational modulation of morphology is very important for functional coordination polymers (CPs) micro/nanostructures, and new strategies are still desired to achieve this challenging target. Herein, organic solvents have been established as the capping agents for rapid modulating the growth of metal-carboxylates CPs in organic solvent/water mixtures at ambient conditions. Co-3,5-pyridinedicarboxylate (pydc) CPs was studied here as the example. During the reaction, the organic solvents exhibited three types of modulation effect: anisotropic growth, anisotropic growth/formation of new crystalline phase and the formation of new crystalline phase solely, which was due to the variation of their binding ability with metal cations. The following study revealed that the binding ability was critically affected by their functional groups and molecular size. Moreover, their modulation effect could be finely tuned by changing volume ratios of solvent mixtures. Furthermore, they could be applied for modulating other metal-carboxylates CPs: Co-1,3,5-benzenetricarboxylic (BTC), Zn-pydc and Eu-pydc etc. Additionally, the as-prepared Co-pydc CPs showed a fascinating morphology-dependent antiferromagnetic behavior.

Solvent induced rapid modulation of micro/nano structures of metal carboxylates coordination polymers: mechanism and morphology dependent magnetism

NASA Astrophysics Data System (ADS)

Liu, Kun; Shen, Zhu-Rui; Li, Yue; Han, Song-De; Hu, Tong-Liang; Zhang, Da-Shuai; Bu, Xian-He; Ruan, Wen-Juan

2014-08-01

Rational modulation of morphology is very important for functional coordination polymers (CPs) micro/nanostructures, and new strategies are still desired to achieve this challenging target. Herein, organic solvents have been established as the capping agents for rapid modulating the growth of metal-carboxylates CPs in organic solvent/water mixtures at ambient conditions. Co-3,5-pyridinedicarboxylate (pydc) CPs was studied here as the example. During the reaction, the organic solvents exhibited three types of modulation effect: anisotropic growth, anisotropic growth/formation of new crystalline phase and the formation of new crystalline phase solely, which was due to the variation of their binding ability with metal cations. The following study revealed that the binding ability was critically affected by their functional groups and molecular size. Moreover, their modulation effect could be finely tuned by changing volume ratios of solvent mixtures. Furthermore, they could be applied for modulating other metal-carboxylates CPs: Co-1,3,5-benzenetricarboxylic (BTC), Zn-pydc and Eu-pydc etc. Additionally, the as-prepared Co-pydc CPs showed a fascinating morphology-dependent antiferromagnetic behavior.

Solvent induced rapid modulation of micro/nano structures of metal carboxylates coordination polymers: mechanism and morphology dependent magnetism

PubMed Central

Liu, Kun; Shen, Zhu-Rui; Li, Yue; Han, Song-De; Hu, Tong-Liang; Zhang, Da-Shuai; Bu, Xian-He; Ruan, Wen-Juan

2014-01-01

Rational modulation of morphology is very important for functional coordination polymers (CPs) micro/nanostructures, and new strategies are still desired to achieve this challenging target. Herein, organic solvents have been established as the capping agents for rapid modulating the growth of metal-carboxylates CPs in organic solvent/water mixtures at ambient conditions. Co-3,5-pyridinedicarboxylate (pydc) CPs was studied here as the example. During the reaction, the organic solvents exhibited three types of modulation effect: anisotropic growth, anisotropic growth/formation of new crystalline phase and the formation of new crystalline phase solely, which was due to the variation of their binding ability with metal cations. The following study revealed that the binding ability was critically affected by their functional groups and molecular size. Moreover, their modulation effect could be finely tuned by changing volume ratios of solvent mixtures. Furthermore, they could be applied for modulating other metal-carboxylates CPs: Co-1,3,5-benzenetricarboxylic (BTC), Zn-pydc and Eu-pydc etc. Additionally, the as-prepared Co-pydc CPs showed a fascinating morphology-dependent antiferromagnetic behavior. PMID:25113225

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.

Liquid-liquid extraction of ethanol from aqueous solutions with amyl acetate, benzyl alcohol, and methyl isobutyl ketone at 298. 15. Kappa

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

Solimo, H.N.; Martinez, H.E.; Riggio, R.

1989-04-01

Experimental mutual solubility and tie-line data were determined for three ternary liquid-liquid systems containing water, ethanol, and amyl acetate, benzyl alcohol, and methyl isobutyl ketone at 298.15{Kappa} in order to obtain their complete phase diagrams and to determine which is the most suitable solvent for extraction of ethanol from aqueous solutions. Tie lines were determined correlating the density of the binodal curve as a function of composition and the plait points using the Othmer and Tobias method. The experimental data were also correlated with the UNIFAC group contribution method. A qualitative agreement was obtained. Experimental results show that amyl acetatemore » is a better solvent than methyl isobutyl ketone and benzyl alcohol.« less

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

PubMed

Peng, Xiaojun; Pang, Jinshan; Deng, Aihua

2011-12-01

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

Integration of whole-cell reaction and product isolation: Highly hydrophobic solvents promote in situ substrate supply and simplify extractive product isolation.

PubMed

Leis, Dorothea; Lauß, Bernhard; Macher-Ambrosch, Robert; Pfennig, Andreas; Nidetzky, Bernd; Kratzer, Regina

2017-09-10

Product isolation from aqueous-organic reaction mixtures that contain high concentrations of whole cells constitutes a challenging task in bioprocessing. Stirring of the biphasic reaction media leads to the formation of solvent droplets coated by cells and other surface active components and an emulsion forms. We used an early focus on phase separation to simplify a whole-cell bioreduction. Octanol, heptanol, hexanol, hexane and dipropylether were tested as co-solvents in the E. coli catalyzed reduction of o-chloroacetophenone. All solvents showed very similar performance in bioreductions and highest yields were obtained with low organic-to-aqueous phase ratios. Reaction mixtures were directly investigated for organic-phase recovery. Phase separation was optimized in small-scale settling experiments and confirmed by the isolation of 20.4g (S)-1-(2-chlorophenyl)ethanol from a 0.5L batch reduction containing 40g CDW /L whole-cell catalyst. Solvent consumption during product isolation could be halved by the simple addition of sodium hydroxide prior to product extraction. Basification to pH 13.5 and three extraction steps with a total of 1.2v/v hexane led to an isolated yield of 87% (97% reduction yield). A general emulsion destabilizing effect under harsh conditions, as extreme pH values and presence of toxic reactants, was observed. Copyright © 2016 The Authors. Published by Elsevier B.V. All rights reserved.

The Ferguson principle and an analysis of biological activity of gases and vapors.

PubMed

Abraham, M H; Nielsen, G D; Alarie, Y

1994-05-01

The Ferguson principle, that Pnar/PO (Pnar is the partial pressure of a series of compounds giving rise to a particular effect on a given system by a physical mechanism, and PO is the saturated vapor pressure of the liquid narcotic) is constant for a series of nonreactive narcotics or toxicants in a given system, is examined and shown to have no thermodynamic basis, contrary to the position of Brink and Posternak. Conditions under which Pnar/PO might be expected to be roughly constant, as an empirical observation, are set out and it is shown that such an observation is consistent with a receptor area in which the liquid narcotic solubilities are roughly constant. An interpretation of relationships between agonist descriptors and biological effects is carried out with three simple biological models. It is shown that the biological potency of nonreactive gases and vapors can be controlled either by an equilibrium between the agonist in the gas phase and the agonist in a receptor or by an equilibrium between the agonist in the gas phase and the agonist in a receptor phase. It is further shown that with the solvation equation of Abraham, solvents can be chosen that mimic the chemical properties of the receptor or receptor phase. For the example of upper respiratory tract irritation of male Swiss OF1 mice, such solvents include N-formylmorpholine, a trialkylphosphate, and wet octanol, but not water itself.

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.

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.

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.

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

NASA Astrophysics Data System (ADS)

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

2017-06-01

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

SOLVENT EXTRACTION PROCESS

DOEpatents

Jonke, A.A.

1957-10-01

In improved solvent extraction process is described for the extraction of metal values from highly dilute aqueous solutions. The process comprises contacting an aqueous solution with an organic substantially water-immiscible solvent, whereby metal values are taken up by a solvent extract phase; scrubbing the solvent extract phase with an aqueous scrubbing solution; separating an aqueous solution from the scrubbed solvent extract phase; and contacting the scrubbed solvent phase with an aqueous medium whereby the extracted metal values are removed from the solvent phase and taken up by said medium to form a strip solution containing said metal values, the aqueous scrubbing solution being a mixture of strip solution and an aqueous solution which contains mineral acids anions and is free of the metal values. The process is particularly effective for purifying uranium, where one starts with impure aqueous uranyl nitrate, extracts with tributyl phosphate dissolved in carbon tetrachloride, scrubs with aqueous nitric acid and employs water to strip the uranium from the scrubbed organic phase.

Spiral Countercurrent Chromatography

PubMed Central

Ito, Yoichiro; Knight, Martha; Finn, Thomas M.

2013-01-01

For many years, high-speed countercurrent chromatography conducted in open tubing coils has been widely used for the separation of natural and synthetic compounds. In this method, the retention of the stationary phase is solely provided by the Archimedean screw effect by rotating the coiled column in the centrifugal force field. However, the system fails to retain enough of the stationary phase for polar solvent systems such as the aqueous–aqueous polymer phase systems. To address this problem, the geometry of the coiled channel was modified to a spiral configuration so that the system could utilize the radially acting centrifugal force. This successfully improved the retention of the stationary phase. Two different types of spiral columns were fabricated: the spiral disk assembly, made by stacking multiple plastic disks with single or four interwoven spiral channels connected in series, and the spiral tube assembly, made by inserting the tetrafluoroethylene tubing into a spiral frame (spiral tube support). The capabilities of these column assemblies were successfully demonstrated by separations of peptides and proteins with polar two-phase solvent systems whose stationary phases had not been well retained in the earlier multilayer coil separation column for high-speed countercurrent chromatography. PMID:23833207

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.

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

PubMed

Englert, Michael; Vetter, Walter

2014-05-16

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

Performance comparison of three types of high-speed counter-current chromatographs for the separation of components of hydrophilic and hydrophobic color additives.

PubMed

Weisz, Adrian; Ito, Yoichiro

2011-09-09

The performance of three types of high-speed counter-current chromatography (HSCCC) instruments was assessed for their use in separating components in hydrophilic and hydrophobic dye mixtures. The HSCCC instruments compared were: (i) a J-type coil planet centrifuge (CPC) system with a conventional multilayer-coil column, (ii) a J-type CPC system with a spiral-tube assembly-coil column, and (iii) a cross-axis CPC system with a multilayer-coil column. The hydrophilic dye mixture consisted of a sample of FD&C Blue No. 2 that contained mainly two isomeric components, 5,5'- and 5,7'-disulfonated indigo, in the ratio of ∼7:1. The hydrophobic dye mixture consisted of a sample of D&C Red No. 17 (mainly Sudan III) and Sudan II in the ratio of ∼4:1. The two-phase solvent systems used for these separations were 1-butanol/1.3M HCl and hexane/acetonitrile. Each of the three instruments was used in two experiments for the hydrophilic dye mixture and two for the hydrophobic dye mixture, for a total of 12 experiments. In one set of experiments, the lower phase was used as the mobile phase, and in the second set of experiments, the upper phase was used as the mobile phase. The results suggest that: (a) use of a J-type instrument with either a multilayer-coil column or a spiral-tube assembly column, applying the lower phase as the mobile phase, is preferable for separating the hydrophilic components of FD&C Blue No. 2; and (b) use of a J-type instrument with multilayer-coil column, while applying either the upper phase or the lower phase as the mobile phase, is preferable for separating the hydrophobic dye mixture of D&C Red No. 17 and Sudan II. Published by Elsevier B.V.

SUPERFUND TREATABILITY CLEARINGHOUSE: FINAL REPORT: DEVELOPMENT OF OPTIMUM TREATMENT SYSTEM FOR WASTEWATER LAGOONS PHASE II - SOLVENT EXTRACTION LABORATORY TESTING

EPA Science Inventory

The U.S. Army surveyed innovative treatment techniques for restoration of hazardous waste lagoons and selected solvent extraction as cost-effective restoration for further study. This treatability study focuses on treatment of organic (explosive) contaminated lagoon sediments w...

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.

Tubing modifications for countercurrent chromatography (CCC): Stationary phase retention and separation efficiency.

PubMed

Englert, Michael; Vetter, Walter

2015-07-16

Countercurrent chromatography (CCC) is a separation technique in which two immiscible liquid phases are used for the preparative purification of synthetic and natural products. In CCC the number of repetitive mixing and de-mixing processes, the retention of the stationary phase and the mass transfer between the liquid phases are significant parameters that influence the resolution and separation efficiency. Limited mass transfer is the main reason for peak broadening and a low number of theoretical plates along with impaired peak resolution in CCC. Hence, technical improvements with regard to column design and tubing modifications is an important aspect to enhance mixing and mass transfer. In this study we constructed a crimping tool which allowed us to make reproducible, semi-automated modifications of conventional round-shaped tubing. Six crimped tubing modifications were prepared, mounted onto multilayer coils which were subsequently installed in the CCC system. The stationary phase retention of the tubing modifications were compared to the conventional system with unmodified tubing in a hydrophobic, an intermediate and a hydrophilic two-phase solvent system. Generally, the tubing modifications provided higher capabilities to retain the stationary phase depending on the solvent system and flow rates. In the intermediate solvent system the separation efficiency was evaluated with a mixture of six alkyl p-hydroxybenzoates. The peak resolution could be increased up to 50% with one of the tubing modifications compared to the unmodified tubing. Using the most convincing tubing modification at fixed values for the stationary phase retention, a reasonable comparison to the unmodified tubing was achieved. The peak width could be reduced up to 49% and a strong positive impact at increased flow rates regarding peak resolution and theoretical plate number was observed compared to unmodified tubing. It could be concluded that the tubing modification enhanced the interphase mixing and mass transfer of the two phases by additional and more vigorous agitation. Copyright © 2015 Elsevier B.V. All rights reserved.

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.

Alleviating monoterpene toxicity using a two-phase extractive fermentation for the bioproduction of jet fuel mixtures in Saccharomyces cerevisiae.

PubMed

Brennan, Timothy C R; Turner, Christopher D; Krömer, Jens O; Nielsen, Lars K

2012-10-01

Monoterpenes are a diverse class of compounds with applications as flavors and fragrances, pharmaceuticals and more recently, jet fuels. Engineering biosynthetic pathways for monoterpene production in microbial hosts has received increasing attention. However, monoterpenes are highly toxic to many microorganisms including Saccharomyces cerevisiae, a widely used industrial biocatalyst. In this work, the minimum inhibitory concentration (MIC) for S. cerevisiae was determined for five monoterpenes: β-pinene, limonene, myrcene, γ-terpinene, and terpinolene (1.52, 0.44, 2.12, 0.70, 0.53 mM, respectively). Given the low MIC for all compounds tested, a liquid two-phase solvent extraction system to alleviate toxicity during fermentation was evaluated. Ten solvents were tested for biocompatibility, monoterpene distribution, phase separation, and price. The solvents dioctyl phthalate, dibutyl phthalate, isopropyl myristate, and farnesene showed greater than 100-fold increase in the MIC compared to the monoterpenes in a solvent-free system. In particular, the MIC for limonene in dibutyl phthalate showed a 702-fold (308 mM, 42.1 g L(-1) of limonene) improvement while cell viability was maintained above 90%, demonstrating that extractive fermentation is a suitable tool for the reduction of monoterpene toxicity. Finally, we estimated that a limonane to farnesane ratio of 1:9 has physicochemical properties similar to traditional Jet-A aviation fuel. Since farnesene is currently produced in S. cerevisiae, its use as a co-product and extractant for microbial terpene-based jet fuel production in a two-phase system offers an attractive bioprocessing option. Copyright © 2012 Wiley Periodicals, Inc.

Demonstration of Advanced CO 2 Capture Process Improvements for Coal-Fired Flue Gas

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

Carroll, John

This document summarizes the activities of Cooperative Agreement DE-FE0026590, “Demonstration of Advanced CO 2 Capture Process Improvements for Coal-Fired Flue Gas” during the performance period of October 1, 2015 through May 31, 2017. This project was funded by the U.S. Department of Energy (DOE) National Energy Technology Laboratory (NETL). Southern Company Services, Inc. (SCS) was the prime contractor and co-funder of the project. Mitsubishi Heavy Industries America (MHIA) and AECOM were project team members. The overall project objective was to improve costs, energy requirements, and performance of an existing amine-based CO 2 capture process. This will occur via improvements inmore » three areas: 1. Reboiler design – The first objective of the program was to demonstrate performance of an integrated stripper/reboiler (termed Built-in Reboiler, or BIR) to reduce footprint, capital costs, and integration issues of the current technology. 2. Particulate management – The second objective was to carry out a Particulate Matter Management (PMM) test. This has the potential to reduce operating costs and capital costs due to the reduced or eliminated need for mechanical filtration. 3. Solvent – The third objective was to carry out a new solvent test plan (referred to as NSL) to demonstrate a new solvent (termed New Solvent A), which is expected to reduce regeneration steam. The bulk price is also expected to be lower than KS-1, which is the current solvent used in this process. NSL testing would include baseline testing, optimization, long term testing, solvent reclamation testing, and final inspection. These combine to form the Advanced Carbon Capture (ACC) technology. Much of this work will be applicable to generic solvent processes, especially in regards to improved reboiler design, and focused to meet or exceed the DOE’s overall carbon capture performance goals of 90% CO 2 capture rate with 95% CO 2 purity at a cost of $40/tonne of CO 2 by 2025 and at a cost of electricity (COE) 30% less than baseline CO 2 capture approaches by 2030. This project was divided into two phases. Phase 1 is the planning phase, and Phase 2 is the construction, operations, testing, and analysis phase. A down select occurred after Phase 1. Phase 1 activities were carried out during this reporting period, and therefore, Phase 1 activities are solely considered in this report. The project was not selected for Phase 2 funding.« less

Adsorption of flexible polymer chains on a surface: Effects of different solvent conditions

NASA Astrophysics Data System (ADS)

Martins, P. H. L.; Plascak, J. A.; Bachmann, M.

2018-05-01

Polymer chains undergoing a continuous adsorption-desorption transition are studied through extensive computer simulations. A three-dimensional self-avoiding walk lattice model of a polymer chain grafted onto a surface has been treated for different solvent conditions. We have used an advanced contact-density chain-growth algorithm, in which the density of contacts can be directly obtained. From this quantity, the order parameter and its fourth-order Binder cumulant are computed, as well as the corresponding critical exponents and the adsorption-desorption transition temperature. As the number of configurations with a given number of surface contacts and monomer-monomer contacts is independent of the temperature and solvent conditions, it can be easily applied to get results for different solvent parameter values without the need of any extra simulations. In analogy to continuous magnetic phase transitions, finite-size-scaling methods have been employed. Quite good results for the critical properties and phase diagram of very long single polymer chains have been obtained by properly taking into account the effects of corrections to scaling. The study covers all solvent effects, going from the limit of super-self-avoiding walks, characterized by effective monomer-monomer repulsion, to poor solvent conditions that enable the formation of compact polymer structures.

Matrix solid-phase dispersion extraction of sulfonamides from blood.

PubMed

Zhang, Yupu; Xu, Xu; Liu, He; Zhai, Yujuan; Sun, Ye; Sun, Shuo; Zhang, Hanqi; Yu, Aimin; Wang, Yinghua

2012-02-01

Matrix solid-phase dispersion extraction was applied to the extraction of sulfadiazine, sulfamerazine, and sulfamethazine from human and animal bloods. The separation and determination of the analytes were carried out by high-performance liquid chromatography. The effects of the types of the dispersion adsorbents and elution solvents were investigated, and the highest recovery was obtained when diatomaceous earth was used as the dispersion adsorbent, while acetone was used as the elution solvent. Under the optimal conditions, the linear range for determining the sulfonamides in blood samples was 0.020-10.0 µg/mL, and the average recoveries of the three sulfonamides were higher than 87.5%.

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

PubMed

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

2017-02-01

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

Study of polymorphic control in an ethanol-water binary solvent

NASA Astrophysics Data System (ADS)

Kitano, Hiroshi; Tanaka, Takayuki; Hirasawa, Izumi

2017-07-01

Three polymorphs of L-Citrulline crystals, anhydrate (Form α, γ and δ) and pseudo polymorph (dihydrate), were confirmed. In this study, polymorphic control of L-Citrulline was attempted by changing the ethanol concentration in ethanol-water binary solvents. First, each polymorph of L-Citrulline crystals was added to the prepared ethanol-water binary solvents and samples which were obtained chronologically were measured by XRD. Also, the crystal sizes and shapes in transformation were observed by microscope. Then, polymorphs of the crystals after transformation were determined by XRD pattern. As a result, the transformation from dihydrate to anhydrate was observed by adding dihydrate crystals to the ethanol-water binary solvent. Similarly, the transformation from anhydrate to another anhydrate was observed. Especially in the case of adding dihydrate, the existences of all polymorphs were confirmed by adjusting ethanol-water binary solvent. According to the results, it was revealed that polymorphic transformation was affected by the trace amount of water contained in ethanol-water binary solvent. Moreover, transformation from dihydrate to anhydrate was constructed with three phases, dissolution of dihydrate, nucleation and growth of anhydrate. Therefore, the solution-mediated polymorphic transformation was supposed to be a key mechanism for this transformation.

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

PubMed

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

2018-05-25

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

Dynamic Stacking Pathway of Perylene Dimers in Aromatic and Nonaromatic Solvents.

PubMed

Hollfelder, Manuel; Gekle, Stephan

2015-08-13

Using molecular dynamics simulations, we elucidate in detail the dynamics of the π-π stacking process of a perylene bisimide (PBI) dimer solvated in toluene. Our calculations show that the transition from the open (unstacked) to the stacked configuration is hindered by a small free energy barrier of approximately 1kBT in toluene but not in the nonaromatic solvent hexane. A similar effect is observed tor two non-covalently linked monomers. The origin of this barrier is traced back to π-π interactions between perylene and the aromatic solvent which are very similar in nature to those between two PBI monomers. The stacking process proceeds in three phases via two well-defined transition states: (i) in the first phase, the two PBI molecules share part of their respective solvation shells forming the first transition state. Further approach needs to squeeze out the shared solvent layer, thus creating the energy barrier. (ii) After removal of the separating solvent, the two PBIs form a second transition state with one monomer located at a random position in the other's solvation shell. (iii) Finally, the two PBIs slide on top of each other into their final stacked position.

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.

Process for separating dissolved solids from a liquid using an anti-solvent and multiple effect evaporators

DOEpatents

Daniels, Edward J.; Jody, Bassam J.; Bonsignore, Patrick V.

1994-01-01

A process and system for treating aluminum salt cake containing water soluble halide salts by contacting the salt cake with water to dissolve water soluble halide salts forming a saturated brine solution. Transporting a portion of about 25% of the saturated brine solution to a reactor and introducing into the saturated brine solution at least an equal volume of a water-miscible low-boiling organic material such as acetone to precipitate a portion of the dissolved halide salts forming a three-phase mixture of an aqueous-organic-salt solution phase and a precipitated salt phase and an organic rich phase. The precipitated salt phase is separated from the other phases and the organic rich phase is recycled to the reactor. The remainder of the saturated brine solution is sent to a multiple effect evaporator having a plurality of stages with the last stage thereof producing low grade steam which is used to boil off the organic portion of the solution which is recycled.

Process for separating dissolved solids from a liquid using an anti-solvent and multiple effect evaporators

DOEpatents

Daniels, E.J.; Jody, B.J.; Bonsignore, P.V.

1994-07-19

A process and system are disclosed for treating aluminum salt cake containing water soluble halide salts by contacting the salt cake with water to dissolve water soluble halide salts forming a saturated brine solution. Transporting a portion of about 25% of the saturated brine solution to a reactor and introducing into the saturated brine solution at least an equal volume of a water-miscible low-boiling organic material such as acetone to precipitate a portion of the dissolved halide salts forming a three-phase mixture of an aqueous-organic-salt solution phase and a precipitated salt phase and an organic rich phase. The precipitated salt phase is separated from the other phases and the organic rich phase is recycled to the reactor. The remainder of the saturated brine solution is sent to a multiple effect evaporator having a plurality of stages with the last stage thereof producing low grade steam which is used to boil off the organic portion of the solution which is recycled. 3 figs.

SISGR: Linking Ion Solvation and Lithium Battery Electrolyte Properties

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

Trulove, Paul C.; Foley, Matthew P.

2012-09-30

The solvation and phase behavior of the model battery electrolyte salt lithium trifluoromethanesulfonate (LiCF 3SO 3) in commonly used organic solvents; ethylene carbonate (EC), gamma-butyrolactone (GBL), and propylene carbonate (PC) was explored. Data from differential scanning calorimetry (DSC), Raman spectroscopy, and X-ray diffraction were correlated to provide insight into the solvation states present within a sample mixture. Data from DSC analyses allowed the construction of phase diagrams for each solvent system. Raman spectroscopy enabled the determination of specific solvation states present within a solvent-salt mixture, and X-ray diffraction data provided exact information concerning the structure of a solvates that couldmore » be isolated Thermal analysis of the various solvent-salt mixtures revealed the phase behavior of the model electrolytes was strongly dependent on solvent symmetry. The point groups of the solvents were (in order from high to low symmetry): C2V for EC, CS for GBL, and C1 for PC(R). The low symmetry solvents exhibited a crystallinity gap that increased as solvent symmetry decreased; no gap was observed for EC-LiTf, while a crystallinity gap was observed spanning 0.15 to 0.3 mole fraction for GBL-LiTf, and 0.1 to 0.33 mole fraction for PC(R)-LiTf mixtures. Raman analysis demonstrated the dominance of aggregated species in almost all solvent compositions. The AGG and CIP solvates represent the majority of the species in solutions for the more concentrated mixtures, and only in very dilute compositions does the SSIP solvate exist in significant amounts. Thus, the poor charge transport characteristics of CIP and AGG account for the low conductivity and transport properties of LiTf and explain why is a poor choice as a source of Li + ions in a Li-ion battery.« less

Electromagnetic mixed waste processing system for asbestos decontamination

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

Kasevich, R.S.; Vaux, W.; Ulerich, N.

The overall objective of this three-phase program is to develop an integrated process for treating asbestos-containing material that is contaminated with radioactive and hazardous constituents. The integrated process will attempt to minimize processing and disposal costs. The objectives of Phase 1 were to establish the technical feasibility of asbestos decomposition, inorganic radionuclide nd heavy metal removal, and organic volatilization. Phase 1 resulted in the successful bench-scale demonstration of the elements required to develop a mixed waste treatment process for asbestos-containing material (ACM) contaminated with radioactive metals, heavy metals, and organics. Using the Phase 1 data, a conceptual process was developed.more » The Phase 2 program, currently in progress, is developing an integrated system design for ACM waste processing. The Phase 3 program will target demonstration of the mixed waste processing system at a DOE facility. The electromagnetic mixed waste processing system employs patented technologies to convert DOE asbestos to a non-hazardous, radionuclide-free, stable waste. The dry, contaminated asbestos is initially heated with radiofrequency energy to remove organic volatiles. Second,the radionuclides are removed by solvent extraction coupled with ion exchange solution treatment. Third, the ABCOV method converts the asbestos to an amorphous silica suspension at low temperature (100{degrees}C). Finally the amorphous silica is solidified for disposal.« less

Purification of α-glucosidase from mouse intestine by countercurrent chromatography coupled with a reverse micelle solvent system.

PubMed

He, Kai; Zou, Zongyao; Hu, Yinran; Yang, Yong; Xiao, Yubo; Gao, Pincao; Li, Xuegang; Ye, Xiaoli

2016-02-01

Countercurrent chromatography coupled with a reverse micelle solvent was applied to separate α-glucosidase, which is stable at pH 6.0-8.8, 15-50°C. The separation conditions are as follows: stationary phase: pH 4.0 Tris-HCl buffer phase containing 50 mM Tris-HCl and 50 mM KCl; mobile phase A: isooctane containing 50 mM anionic surfactant sodium di(2-ethylhexyl)sulfosuccinate; mobile phase B: 50 mM Tris-HCl buffer containing 500 mM KCl (pH 8.0); In total, 25 mL (23.9 mg) crude enzyme was injected through the injection valve, the enzymatic reaction and sodium dodecylsulfate polyacrylamide gel electrophoresis results imply that the activity of purified α-glucosidase is 6.63-fold higher than that of the crude enzyme. Therefore, countercurrent chromatography coupled with a reverse micelle solvent is capable for protein separation and enrichment. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fabrication of Janus particles composed of poly (lactic-co-glycolic) acid and hard fat using a solvent evaporation method.

PubMed

Matsumoto, Akihiro; Murao, Satoshi; Matsumoto, Michiko; Watanabe, Chie; Murakami, Masahiro

The feasibility of fabricating Janus particles based on phase separation between a hard fat and a biocompatible polymer was investigated. The solvent evaporation method used involved preparing an oil-in-water (o/w) emulsion with a mixture of poly (lactic-co-glycolic) acid (PLGA), hard fat, and an organic solvent as the oil phase and a polyvinyl alcohol aqueous solution as the water phase. The Janus particles were formed when the solvent was evaporated to obtain certain concentrations of PLGA and hard fat in the oil phase, at which phase separation was estimated to occur based on the phase diagram analysis. The hard fat hemisphere was proven to be the oil phase using a lipophilic dye Oil Red O. When the solvent evaporation process was performed maintaining a specific volume during the emulsification process; Janus particles were formed within 1.5 h. However, the formed Janus particles were destroyed by stirring for over 6 h. In contrast, a few Janus particles were formed when enough water to dissolve the oil phase solvent was added to the emulsion immediately after the emulsification process. The optimized volume of the solvent evaporation medium dominantly formed Janus particles and maintained the conformation for over 6 h with stirring. These results indicate that the formation and stability of Janus particles depend on the rate of solvent evaporation. Therefore, optimization of the solvent evaporation rate is critical to obtaining stable PLGA and hard fat Janus particles.

Modifier mass transfer kinetic effect in the performance of solvent gradient simulated moving bed (SG-SMB) process

NASA Astrophysics Data System (ADS)

Câmara, L. D. T.

2015-09-01

The solvent-gradient simulated moving bed process (SG-SMB) is the new tendency in the performance improvement if compared to the traditional isocratic solvent conditions. In such SG-SMB separation process the modulation of the solvent strength leads to significant increase in the purities and productivity followed by reduction in the solvent consumption. A stepwise modelling approach was utilized in the representation of the interconnected chromatographic columns of the system combined with lumped mass transfer models between the solid and liquid phase. The influence of the solvent modifier was considered applying the Abel model which takes into account the effect of modifier volume fraction over the partition coefficient. The modelling and simulations were carried out and compared to the experimental SG-SMB separation of the amino acids phenylalanine and tryptophan. A lumped mass transfer kinetic model was applied for both the modifier (ethanol) as well as the solutes. The simulation results showed that such simple and global mass transfer models are enough to represent all the mass transfer effect between the solid adsorbent and the liquid phase. The separation performance can be improved reducing the interaction or the mass transfer kinetic effect between the solid adsorbent phase and the modifier. The simulations showed great agreement fitting the experimental data of the amino acids concentrations both at the extract as well as at the raffinate.

Antisolvent membrane crystallization of pharmaceutical compounds.

PubMed

Di Profio, Gianluca; Stabile, Carmen; Caridi, Antonella; Curcio, Efrem; Drioli, Enrico

2009-12-01

This article describes a modification of the conventional membrane crystallization technique in which a membrane is used to dose the solvent/antisolvent composition to generate supersaturation and induce crystallization in a drug solution. Two operative configurations are proposed: (a) solvent/antisolvent demixing crystallization, where the solvent is removed in at higher flow rate than the antisolvent so that phase inversion promotes supersaturation and (b) antisolvent addition, in which the antisolvent is dosed into the crystallizing drug solution. In both cases, solvent/antisolvent migration occurs in vapor phase and it is controlled by the porous membrane structure, acting on the operative process parameters. This mechanism is different than that observed when forcing the liquid phases through the pores and the more finely controllable supersaturated environment would generate crystals with the desired characteristics. Two organic molecules of relevant industrial implication, like paracetamol and glycine, were used to test the new systems. Experiments demonstrated that, by using antisolvent membrane crystallization in both configurations, accurate control of solution composition at the crystallization point has been achieved with effects on crystals morphology. 2009 Wiley-Liss, Inc. and the American Pharmacists Association

Measuring in vitro biotransformation rates of super hydrophobic chemicals in rat liver s9 fractions using thin-film sorbent-phase dosing.

PubMed

Lee, Yung-Shan; Otton, S Victoria; Campbell, David A; Moore, Margo M; Kennedy, Chris J; Gobas, Frank A P C

2012-01-03

Methods for rapid and cost-effective assessment of the biotransformation potential of very hydrophobic and potentially bioaccumulative chemicals in mammals are urgently needed for the ongoing global evaluation of the environmental behavior of commercial chemicals. We developed and tested a novel solvent-free, thin-film sorbent-phase in vitro dosing system to measure the in vitro biotransformation rates of very hydrophobic chemicals in male Sprague-Dawley rat liver S9 homogenates and compared the rates to those measured by conventional solvent-delivery dosing. The thin-film sorbent-phase dosing system using ethylene vinyl acetate coated vials was developed to eliminate the incomplete dissolution of very hydrophobic substances in largely aqueous liver homogenates, to determine biotransformation rates at low substrate concentrations, to measure the unbound fraction of substrate in solution, and to simplify chemical analysis by avoiding the difficult extraction of test chemicals from complex biological matrices. Biotransformation rates using sorbent-phase dosing were 2-fold greater than those measured using solvent-delivery dosing. Unbound concentrations of very hydrophobic test chemicals were found to decline with increasing S9 and protein concentrations, causing measured biotransformation rates to be independent of S9 or protein concentrations. The results emphasize the importance of specifying both protein content and unbound substrate fraction in the measurement and reporting of in vitro biotransformation rates of very hydrophobic substances, which can be achieved in a thin-film sorbent-phase dosing system.

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

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.

Biscalix[4]arene derivative as a very efficient phase selective gelator for oil spill recovery.

PubMed

Tsai, Chia-Chen; Cheng, Ying-Tsai; Shen, Li-Ching; Chang, Kai-Chi; Ho, I-Ting; Chu, Jean-Ho; Chung, Wen-Sheng

2013-11-15

A biscalixarene framework, without long alkyl chains, has been readily synthesized in three steps starting from the parent calix[4]arene. The biscalix[4]arene 1 was able to form organogels in various alcoholic solvents; furthermore, it exhibited an excellent phase selective gelation property that is potentially useful in oil spill recovery.

Immobilizing Highly Catalytically Active Pt Nanoparticles inside the Pores of Metal-Organic Framework: A Double Solvents Approach

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

Aijaz, Arshad; Karkamkar, Abhijeet J.; Choi, Young Joon

2012-08-29

Ultrafine Pt nanoparticles were successfully immobilized inside the pores of a metal-organic framework MIL-101 without deposition of Pt nanoparticles on the external surfaces of framework by using a 'double solvents' method. The resulting Pt@MIL-101 composites with different Pt loadings represent the first highly active MOF-immobilized metal nanocatalysts for catalytic reactions in all three phases: liquid-phase ammonia borane hydrolysis; solid-phase ammonia borane thermal dehy-drogenation and gas-phase CO oxidation. The observed excellent catalytic performances are at-tributed to the small Pt nanoparticles within the pores of MIL-101. 'We are thankful to AIST and METI for financial support. TA & AK are thankful formore » support from the US Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. PNNL is operated by Battelle.'« less

21 CFR 862.2270 - Thin-layer chromatography system for clinical use.

Code of Federal Regulations, 2011 CFR

2011-04-01

... a mixture. The mixture of compounds is absorbed onto a stationary phase or thin layer of inert material (e.g., cellulose, alumina, etc.) and eluted off by a moving solvent (moving phase) until equilibrium occurs between the two phases. (b) Classification. Class I (general controls). The device is...

Room-temperature ionic liquids as replacements for organic solvents in multiphase bioprocess operations.

PubMed

Cull, S G; Holbrey, J D; Vargas-Mora, V; Seddon, K R; Lye, G J

2000-07-20

Organic solvents are widely used in a range of multiphase bioprocess operations including the liquid-liquid extraction of antibiotics and two-phase biotransformation reactions. There are, however, considerable problems associated with the safe handling of these solvents which relate to their toxic and flammable nature. In this work we have shown for the first time that room-temperature ionic liquids, such as 1-butyl-3-methylimi- dazolium hexafluorophosphate, [bmim][PF(6)], can be successfully used in place of conventional solvents for the liquid-liquid extraction of erythromycin-A and for the Rhodococcus R312 catalyzed biotransformation of 1, 3-dicyanobenzene (1,3-DCB) in a liquid-liquid, two-phase system. Extraction of erythromycin with either butyl acetate or [bmim][PF(6)] showed that values of the equilibrium partition coefficient, K, up to 20-25 could be obtained for both extractants. The variation of K with the extraction pH was also similar in the pH range 5-9 though differed significantly at higher pH values. Biotransformation of 1,3-DCB in both water-toluene and water-[bmim][PF(6)] systems showed similar profiles for the conversion of 1,3-DCB initially to 3-cyanobenzamide and then 3-cyanobenzoic acid. The initial rate of 3-cyanobenzamide production in the water-[bmim][PF(6)] system was somewhat lower, however, due to the reduced rate of 1,3-DCB mass transfer from the more viscous [bmim] [PF(6)] phase. It was also shown that the specific activity of the biocatalyst in the water-[bmim] [PF(6)] system was almost an order of magnitude greater than in the water-toluene system which suggests that the rate of 3-cyanobenzamide production was limited by substrate mass transfer rather than the activity of the biocatalyst. Copyright 2000 John Wiley & Sons, Inc.

Procedure for chromatography involving sample solvent with higher elution strength than the mobile phase.

PubMed

Patil, Nitin S; Mendhe, Rakesh B; Sankar, Ajeet A; Iyer, Harish

2008-01-11

In preparative chromatography, often the solubility of the sample in the mobile phase is limited, making the mobile phase unsuitable as a solvent for preparation of load. Generally, solvents that have high solubility for the sample also have higher elution strengths than the mobile phase. Additionally, at high loading volumes, these strong sample solvents are known to adversely affect the band profiles leading to poor chromatographic performance. Here, we show that controlling the mobile phase strength during loading and post-load elution resulted in improved band profiles when the sample solvent was stronger than the mobile phase. Such an approach improves performance in preparative chromatography by allowing either higher sample loading or higher organic content in mobile phase (without loss of yield). Alternately, the approach can be used for improvement in performance by increase in yield or product purity.

Phase Behavior of Three PBX Elastomers in High-Pressure Chlorodifluoromethane

NASA Astrophysics Data System (ADS)

Lee, Byung-Chul

2017-10-01

The phase equilibrium behavior data are presented for three kinds of commercial polymer-bonded explosive (PBX) elastomers in chlorodifluoromethane (HCFC22). Levapren^{{registered }} ethylene- co-vinyl acetate (LP-EVA), HyTemp^{{registered }} alkyl acrylate copolymer (HT-ACM), and Viton^{{registered }} fluoroelastomer (VT-FE) were used as the PBX elastomers. For each elastomer + HCFC22 system, the cloud point (CP) and/or bubble point (BP) pressures were measured while varying the temperature and elastomer composition using a phase equilibrium apparatus fitted with a variable-volume view cell. The elastomers examined in this study indicated a lower critical solution temperature phase behavior in the HCFC22 solvent. LP-EVA showed the CPs at temperatures of 323 K to 343 K and at pressures of 3 MPa to 10 MPa, whereas HT-ACM showed the CPs at conditions between 338 K and 363 K and between 4 MPa and 12 MPa. For the LP-EVA and HT-ACM elastomers, the BP behavior was observed at temperatures below about 323 K. For the VT-FE + HCFC22 system, only the CP behavior was observed at temperatures between 323 K and 353 K and at pressures between 6 MPa and 21 MPa. As the elastomer composition increased, the CP pressure increased, reached a maximum value at a specific elastomer composition, and then remained almost constant.

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

NASA Astrophysics Data System (ADS)

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

2018-04-01

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

Enantioseparation of omeprazole--effect of different packing particle size on productivity.

PubMed

Enmark, Martin; Samuelsson, Jörgen; Forssén, Patrik; Fornstedt, Torgny

2012-06-01

Enantiomeric separation of omeprazole has been extensively studied regarding both product analysis and preparation using several different chiral stationary phases. In this study, the preparative chiral separation of omeprazole is optimized for productivity using three different columns packed with amylose tris (3,5-dimethyl phenyl carbamate) coated macroporous silica (5, 10 and 25 μm) with a maximum allowed pressure drop ranging from 50 to 400 bar. This pressure range both covers low pressure process systems (50-100 bar) and investigates the potential for allowing higher pressure limits in preparative applications in a future. The process optimization clearly show that the larger 25 μm packing material show higher productivity at low pressure drops whereas with increasing pressure drops the smaller packing materials have substantially higher productivity. Interestingly, at all pressure drops, the smaller packing material result in lower solvent consumption (L solvent/kg product); the higher the accepted pressure drop, the larger the gain in reduced solvent consumption. The experimental adsorption isotherms were not identical for the different packing material sizes; therefore all calculations were recalculated and reevaluated assuming identical adsorption isotherms (with the 10 μm isotherm as reference) which confirmed the trends regarding productivity and solvent consumption. Copyright © 2012 Elsevier B.V. All rights reserved.

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).

A 1:1 pharmaceutical cocrystal of myricetin in combination with uncommon piracetam conformer: X-ray single crystal analysis and mechanochemical synthesis

NASA Astrophysics Data System (ADS)

Sowa, Michał; Ślepokura, Katarzyna; Matczak-Jon, Ewa

2014-01-01

Combination of two Active Pharmaceutical Ingredients, myricetin and piracetam, yields a 1:1 cocrystal characterized by X-ray single-crystal and powder diffraction, Raman spectroscopy, 1H NMR, thermal analysis (DSC and TG-DTA) methods. Constituents of the cocrystalline phase were also investigated in terms of Hirshfeld surfaces. Compounds in their neutral forms cocrystallize in the Pna21 space group of orthorhombic system. Notably, piracetam adopts an uncommon conformation, not encountered in its cocrystals previously described. In the crystal lattice, a three-dimensional hydrogen-bonded network is observed, including formation of a 2D molecular scaffolding motif. A scale-up procedure is readily available with use of solvent-drop grinding method, in which application of a variety of common solvents leads to formation of the cocrystal, as confirmed by XRPD and Raman spectroscopy.

Effects of low urea concentrations on protein-water interactions.

PubMed

Ferreira, Luisa A; Povarova, Olga I; Stepanenko, Olga V; Sulatskaya, Anna I; Madeira, Pedro P; Kuznetsova, Irina M; Turoverov, Konstantin K; Uversky, Vladimir N; Zaslavsky, Boris Y

2017-01-01

Solvent properties of aqueous media (dipolarity/polarizability, hydrogen bond donor acidity, and hydrogen bond acceptor basicity) were measured in the coexisting phases of Dextran-PEG aqueous two-phase systems (ATPSs) containing .5 and 2.0 M urea. The differences between the electrostatic and hydrophobic properties of the phases in the ATPSs were quantified by analysis of partitioning of the homologous series of sodium salts of dinitrophenylated amino acids with aliphatic alkyl side chains. Furthermore, partitioning of eleven different proteins in the ATPSs was studied. The analysis of protein partition behavior in a set of ATPSs with protective osmolytes (sorbitol, sucrose, trehalose, and TMAO) at the concentration of .5 M, in osmolyte-free ATPS, and in ATPSs with .5 or 2.0 M urea in terms of the solvent properties of the phases was performed. The results show unambiguously that even at the urea concentration of .5 M, this denaturant affects partitioning of all proteins (except concanavalin A) through direct urea-protein interactions and via its effect on the solvent properties of the media. The direct urea-protein interactions seem to prevail over the urea effects on the solvent properties of water at the concentration of .5 M urea and appear to be completely dominant at 2.0 M urea concentration.

Nanoporous thermosetting polymers.

PubMed

Raman, Vijay I; Palmese, Giuseppe R

2005-02-15

Potential applications of nanoporous thermosetting polymers include polyelectrolytes in fuel cells, separation membranes, adsorption media, and sensors. Design of nanoporous polymers for such applications entails controlling permeability by tailoring pore size, structure, and interface chemistry. Nanoporous thermosetting polymers are often synthesized via free radical mechanisms using solvents that phase separate during polymerization. In this work, a novel technique for the synthesis of nanoporous thermosets is presented that is based on the reactive encapsulation of an inert solvent using step-growth cross-linking polymerization without micro/macroscopic phase separation. The criteria for selecting such a monomer-polymer-solvent system are discussed based on FTIR analysis, observed micro/macroscopic phase separation, and thermodynamics of swelling. Investigation of resulting network pore structures by scanning electron microscopy (SEM) and small-angle X-ray scattering following extraction and supercritical drying using carbon dioxide showed that nanoporous polymeric materials with pore sizes ranging from 1 to 50 nm can be synthesized by varying the solvent content. The differences in the porous morphology of these materials compared to more common free radically polymerized analogues that exhibit phase separation were evident from SEM imaging. Furthermore, it was demonstrated that the chemical activity of the nanoporous materials obtained by our method could be tailored by grafting appropriate functional groups at the pore interface.

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.

Interpretation of third phase formation in the Th(IV)-HNO{sub3}, TBP-n-octane system with baxter's sticky spheres model.

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

Chiarizia, R.; Jensen, M. P.; Borkowski, M.

2004-01-01

Small-angle neutron scattering (SANS) data for the tri-n-butylphosphate (TBP)-n-octane, HNO{sub 3}-Th(NO{sub 3}){sub 4} solvent extraction system, obtained under a variety of experimental conditions, have been interpreted using two different models. The particle growth model led to unrealistic results. The Baxter model for hard-spheres with surface adhesion, on the other hand, was more successful. According to this model, the increase in scattering intensity in the low Q range observed when increasing amounts of Th(NO{sub 3}){sub 4} are extracted into the organic phase, has been interpreted as arising from interactions between small reverse micelles containing three TBP molecules. Upon extraction of Th(NO{submore » 3}){sub 4}, the micelles interact through attractive forces between their polar cores with a potential energy of up to about 2 k{sub B}T. The intermicellar attraction, under suitable conditions, leads to third phase formation. Upon phase splitting, most of the solutes of the original organic phase separate in a continuous phase containing interspersed layers of n-octane.« less

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

EPA Science Inventory

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

EVALUATION OF ANALYTICAL METHODS FOR DETERMINING PESTICIDES IN BABY FOOD

EPA Science Inventory

Three extraction methods and two detection techniques for determining pesticides in baby food were evaluated. The extraction techniques examined were supercritical fluid extraction (SFE), enhanced solvent extraction (ESE), and solid phase extraction (SPE). The detection techni...

Extraction of three bioactive diterpenoids from Andrographis paniculata: effect of the extraction techniques on extract composition and quantification of three andrographolides using high-performance liquid chromatography.

PubMed

Kumar, Satyanshu; Dhanani, Tushar; Shah, Sonal

2014-10-01

Andrographis paniculata (Burm.f.) wall.ex Nees (Acanthaceae) or Kalmegh is an important medicinal plant finding uses in many Ayurvedic formulations. Diterpenoid compounds andrographolides (APs) are the main bioactive phytochemicals present in leaves and herbage of A. paniculata. The efficiency of supercritical fluid extraction (SFE) using carbon dioxide was compared with the solid-liquid extraction techniques such as solvent extraction, ultrasound-assisted solvent extraction and microwave-assisted solvent extraction with methanol, water and methanol-water as solvents. Also a rapid and validated reverse-phase high-performance liquid chromatography-diode array detection method was developed for the simultaneous determination of the three biologically active compounds, AP, neoandrographolide and andrograpanin, in the extracts of A. paniculata. Under the best SFE conditions tested for diterpenoids, which involved extraction at 60°C and 100 bar, the extractive efficiencies were 132 and 22 µg/g for AP and neoandrographolide, respectively. The modifier percentage significantly affected the extraction efficiency. © The Author [2013]. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

It is all about the solvent: on the importance of the mobile phase for ZIC-HILIC glycopeptide enrichment.

PubMed

Alagesan, Kathirvel; Khilji, Sana Khan; Kolarich, Daniel

2017-01-01

Glycopeptide enrichment is a crucial step in glycoproteomics for which hydrophilic interaction chromatography (HILIC) has extensively been applied due to its low bias towards different glycan types. A systematic evaluation of applicable HILIC mobile phases on glycopeptide enrichment efficiency and selectivity is, to date, however, still lacking. Here, we present a novel, simplified technique for HILIC enrichment termed "Drop-HILIC", which was applied to systematically evaluate the mobile phase effect on ZIC-HILIC (zwitterionic type of hydrophilic interaction chromatography) glycopeptide enrichment. The four most commonly used MS compatible organic solvents were investigated: (i) acetonitrile, (ii) methanol, (iii) ethanol and (iv) isopropanol. Glycopeptide enrichment efficiencies were evaluated for each solvent system using samples of increasing complexity ranging from well-defined synthetic glycopeptides spiked into different concentrations of tryptic BSA peptides, followed by standard glycoproteins, and a complex sample derived from human (depleted and non-depleted) serum. ZIC-HILIC glycopeptide efficiency largely relied upon the used solvent. Different organic mobile phases enriched distinct glycopeptide subsets in a peptide backbone hydrophilicity-dependant manner. Acetonitrile provided the best compromise for the retention of both hydrophilic and hydrophobic glycopeptides, whereas methanol was confirmed to be unsuitable for this purpose. The enrichment efficiency of ethanol and isopropanol towards highly hydrophobic glycopeptides was compromised as considerable co-enrichment of unmodified peptides occurred, though for some hydrophobic glycopeptides isopropanol showed the best enrichment properties. This study shows that even minor differences in the peptide backbone and solvent do significantly influence HILIC glycopeptide enrichment and need to be carefully considered when employed for glycopeptide enrichment. Graphical Abstract The organic solvent plays a crucial role in ZIC-HILIC glycopeptide enrichment.

Formation of indomethacin-saccharin cocrystals using supercritical fluid technology.

PubMed

Padrela, Luis; Rodrigues, Miguel A; Velaga, Sitaram P; Matos, Henrique A; de Azevedo, Edmundo Gomes

2009-08-12

The main objective of the present work is to check the feasibility of supercritical fluid (SCF) technologies in the screening and design of cocrystals (novel crystalline solids). The cocrystal formation tendencies in three different SCF techniques, focusing on distinct supercritical fluid properties - solvent, anti-solvent and atomization enhancer - were investigated. The effect of processing parameters on the cocrystal formation behaviour and particle properties in these techniques was also studied. A recently reported indomethacin-saccharin (IND-SAC) cocrystalline system was our model system. A 1:1 molar ratio of indomethacin (gamma-form) and saccharin was used as a starting material. The SCF techniques employed in the study include the CSS technique (cocrystallization with supercritical solvent), the SAS technique (supercritical anti-solvent), and the AAS technique (atomization and anti-solvent). The resulting cocrystalline phase was identified using differential scanning calorimetry (DSC), powder X-ray diffraction (PXRD), and Fourier transform-Raman (FT-Raman). The particle morphologies and size distributions were determined using scanning electron microscopy (SEM) and aerosizer, respectively. The pure IND-SAC cocrystals were obtained from SAS and AAS processes, whilst partial to no cocrystal formation occurred in the CSS process. However, no remarkable differences were observed in terms of cocrystal formation at different processing conditions in SAS and AAS processes. Particles from CSS processes were agglomerated and large, whilst needle-to-block-shaped and spherical particles were obtained from SAS and AAS processes, respectively. The particle size distribution of these particles was 0.2-5microm. Particulate IND-SAC cocrystals with different morphologies and sizes (nano-to-micron) were produced using supercritical fluid techniques. This work demonstrates the potential of SCF technologies as screening methods for cocrystals with possibilities for particle engineering.

Theory of nematic order with aggregate dehydration for reversibly assembling proteins in concentrated solutions: Application to sickle-cell hemoglobin polymers

NASA Astrophysics Data System (ADS)

Hentschke, Reinhard; Herzfeld, Judith

1991-06-01

The reversible association of globular protein molecules in concentrated solution leads to highly polydisperse fibers, e.g., actin filaments, microtubules, and sickle-cell hemoglobin fibers. At high concentrations, excluded-volume interactions between the fibers lead to spontaneous alignment analogous to that in simple lyotropic liquid crystals. However, the phase behavior of reversibly associating proteins is complicated by the threefold coupling between the growth, alignment, and hydration of the fibers. In protein systems aggregates contain substantial solvent, which may cause them to swell or shrink, depending on osmotic stress. Extending previous work, we present a model for the equilibrium phase behavior of the above-noted protein systems in terms of simple intra- and interaggregate interactions, combined with equilibration of fiber-incorporated solvent with the bulk solvent. Specifically, we compare our model results to recent osmotic pressure data for sickle-cell hemoglobin and find excellent agreement. This comparison shows that particle interactions sufficient to cause alignment are also sufficient to squeeze significant amounts of solvent out of protein fibers. In addition, the model is in accord with findings from independent sedimentation and birefringence studies on sickle-cell hemoglobin.

A Phase Separation Route to Synthesize α-Fe2O3 Porous Nanofibers via Electrospinning for Ultrafast Ethanol Sensing

NASA Astrophysics Data System (ADS)

Dong, Shuwen; Yan, Shuang; Gao, Wenyuan; Liu, Guishan; Hao, Hongshun

2018-07-01

A facile and economic procedure was provided to synthesize α-Fe2O3 nanofibers. In this procedure, porous α-Fe2O3 nanofibers were obtained by a single-polymer/binary-solvent system, while solid α-Fe2O3 nanofibers were prepared by a single-polymer/single-solvent system. The crystal structure and morphology of both samples were characterized by x-ray diffraction, scanning electron microscopy, transmission electron microscopy and nitrogen adsorption/desorption isotherms. The formation mechanism of porous structure was based on solvent evaporation-induced phase separation by the use of mixed solvents with different volatility. Furthermore, ethanol-sensing performance of the porous α-Fe2O3 nanofibers was evaluated and compared with solid α-Fe2O3 nanofibers. Results from gas-sensing measurements reveal that porous α-Fe2O3 nanofibers exhibit higher sensitivity and slightly longer recovery time than solid α-Fe2O3 nanofibers. Over all, the gas sensor based on porous α-Fe2O3 nanofibers shows excellent ethanol-sensing capability with high sensitivity and ultrafast response/recovery behaviors, indicating its potential application as a real-time monitoring gas sensor.

Solvent Extraction Separation of Trivalent Americium from Curium and the Lanthanides

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

Jensen, Mark P.; Chiarizia, Renato; Ulicki, Joseph S.

2015-02-27

The sterically constrained, macrocyclic, aqueous soluble ligand N,N'-bis[(6-carboxy-2-pyridyl)methyl]-1,10-diaza-18-crown-6 (H2BP18C6) was investigated for separating americium from curium and all the lanthanides by solvent extraction. Pairing H2BP18C6, which favors complexation of larger f-element cations, with acidic organophosphorus extractants that favor extraction of smaller f-element cations, such as bis-(2-ethylhexyl)phosphoric acid (HDEHP) or (2-ethylhexyl)phosphonic acid mono(2-ethylhexyl) ester (HEH[EHP]), created solvent extraction systems with good Cm/Am selectivity, excellent trans-lanthanide selectivity (Kex,Lu/Kex,La = 108), but poor selectivity for Am against the lightest lanthanides. However, using an organic phase containing both a neutral extractant, N,N,N’,N’-tetra(2-ethylhexyl)diglycolamide (TEHDGA), and HEH[EHP] enabled rejection of the lightest lanthanides during loading ofmore » the organic phase from aqueous nitric acid, eliminating their interference in the americium stripping stages. In addition, although it is a macrocyclic ligand, H2BP18C6 does not significantly impede the mass transfer kinetics of the HDEHP solvent extraction system« less

A Phase Separation Route to Synthesize α-Fe2O3 Porous Nanofibers via Electrospinning for Ultrafast Ethanol Sensing

NASA Astrophysics Data System (ADS)

Dong, Shuwen; Yan, Shuang; Gao, Wenyuan; Liu, Guishan; Hao, Hongshun

2018-04-01

A facile and economic procedure was provided to synthesize α-Fe2O3 nanofibers. In this procedure, porous α-Fe2O3 nanofibers were obtained by a single-polymer/binary-solvent system, while solid α-Fe2O3 nanofibers were prepared by a single-polymer/single-solvent system. The crystal structure and morphology of both samples were characterized by x-ray diffraction, scanning electron microscopy, transmission electron microscopy and nitrogen adsorption/desorption isotherms. The formation mechanism of porous structure was based on solvent evaporation-induced phase separation by the use of mixed solvents with different volatility. Furthermore, ethanol-sensing performance of the porous α-Fe2O3 nanofibers was evaluated and compared with solid α-Fe2O3 nanofibers. Results from gas-sensing measurements reveal that porous α-Fe2O3 nanofibers exhibit higher sensitivity and slightly longer recovery time than solid α-Fe2O3 nanofibers. Over all, the gas sensor based on porous α-Fe2O3 nanofibers shows excellent ethanol-sensing capability with high sensitivity and ultrafast response/recovery behaviors, indicating its potential application as a real-time monitoring gas sensor.

Fingering dynamics on the adsorbed solute with influence of less viscous and strong sample solvent.

PubMed

Rana, Chinar; Mishra, Manoranjan

2014-12-07

Viscous fingering is a hydrodynamic instability that sets in when a low viscous fluid displaces a high viscous fluid and creates complex patterns in porous media flows. Fundamental facets of the displacement process, such as the solute concentration distribution, spreading length, and the solute mixing, depend strongly on the type of pattern created by the unstable interface of the underlying fluids. In the present study, the frontal interface of the sample shows viscous fingering and the strong solvent causes the retention of the solute to depend on the solvent concentration. This work presents a computational investigation to explore the effect of the underlying physico-chemical phenomena, (i.e., the combined effects of solvent strength, retention, and viscous fingering) on the dynamics of the adsorbed solute. A linear adsorption isotherm has been assumed between the mobile and stationary phases of the solute. We carried out the numerical simulations by considering a rectangular Hele-Shaw cell as an analog to 2D-porous media containing a three component system (displacing fluid, sample solvent, solute) to map out the evolution of the solute concentration. We observed that viscous fingering at the frontal interface of the strong sample solvent intensifies the band broadening of the solute zone. Also notable increase in the spreading dynamics of the solute has been observed for less viscous and strong sample solvent as compared to the high viscous sample slices or in the pure dispersive case. On the contrary, the solute gets intensively mixed at early times for more viscous sample in comparison to less viscous one. The results of the simulations are in qualitative agreement with the behavior observed in the liquid chromatography column experiments.

Extraction of phenol using trialkylphosphine oxides (Cyanex 923) in kerosene

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

Urtiaga, A.M.; Ortiz, I.

1997-04-01

A group of extractants based on phosphine oxides have been reported as an alternative to conventional polar solvents for phenol-liquid-liquid extraction. Among phosphoryl extractants, Cyanex 923 (a mixture of four trialkylphosphine oxides, alkyl = normal, C{sub 6}, C{sub 8}) has proved to combine high extraction efficiency and low water solubility, obviating the necessity of removing the solvent from the aqueous raffinate, a need associated with the use of methyl isobutyl ketone and isopropyl ether, the solvents most widely employed for this application. Phosphoryl extractants are solvating extractants, and are known to form relatively strong and reversible hydrogen bonds with phenols.more » The fact that most of these systems show a strong nonideality in the organic phase makes a general theoretical treatment of the equilibria almost impossible, leading to the necessity of obtaining a large number of data in order to describe the equilibria for design purposes. In this work the effect of the concentration of phenol in the aqueous phase on the partition coefficient for phenol in Cyanex 923-kerosene/water systems is investigated at six different concentrations of the extractant in the organic phase: 1, 5, 10, 20, 50, and 70% v/v of Cyanex 923-kerosene/water systems is investigated at six different concentrations of the extractant in the organic phase: 1, 5, 10, 20, 50, and 70% v/v of Cyanex 923 in kerosene. The initial concentrations of phenol in the aqueous phase were in the 1000 mg/L < C{sub PhOH} < 50,000 mg/L range.« less

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

DOEpatents

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

2014-06-10

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

Two-Phase Extraction for Comprehensive Analysis of the Plant Metabolome by NMR.

PubMed

Schripsema, Jan; Dagnino, Denise

2018-01-01

Metabolomics is the area of research, which strives to obtain complete metabolic fingerprints, to detect differences between them, and to provide hypothesis to explain those differences [1]. But obtaining complete metabolic fingerprints is not an easy task. Metabolite extraction is a key step during this process, and much research has been devoted to finding the best solvent mixture to extract as much metabolites as possible.Here a procedure is described for analysis of both polar and apolar metabolites using a two-phase extraction system. D 2 O and CDCl 3 are the solvents of choice, and their major advantage is that, for the identification of the compounds, standard databases can be used because D 2 O and CDCl 3 are the solvents most commonly used for pure compound NMR spectra. The procedure enables the absolute quantification of components via the addition of suitable internal standards. The extracts are also suitable for further analysis with other systems like LC-MS or GC-MS.

The Role of Solvent-Solute Interactions on The Behavior of Low Molecular Mass Organo-Gelators

NASA Astrophysics Data System (ADS)

Cavicchi, Kevin; Feng, Li

2012-02-01

Low molecular mass organo-gelators (LMOGs) are a class of small molecules that can self-assemble in organic solvents to form three-dimensional fibrillar networks. This has a profound effect on the viscoelastic properties of the solution causing physical gelation. These gels have uses in a range of industries including cosmetics, foodstuffs, plastics, petroleum and pharmaceuticals. A fundamental question in this field is: What makes a good LMOG? This talk will discuss the relationships between the viscoelastic properties and thermodynamic phase behavior of LMOG/solvent solutions. The regular solution model was used to fit the liquidus line and sol/gel transition temperature vs. concentration in different solvents to determine LMOG-solvent interaction parameters (χ = A/T). This parameter A was found to scale with the solubility parameter of the solvent, especially for non-polar solvents. This demonstrates that gelation is strongly linked to LMOG solubility and indicates that the bulk thermodynamic parameters of the LMOG (solubility parameter and melting temperature) are useful to predict the solution behavior of LMOGs.

Separation of Aeruginosin-865 from Cultivated Soil Cyanobacterium (Nostoc sp.) by Centrifugal Partition Chromatography combined with Gel Permeation Chromatography.

PubMed

Cheel, José; Minceva, Mirjana; Urajová, Petra; Aslam, Rabya; Hrouzek, Pavel; Kopecký, Jiří

2015-10-01

Aeruginosin-865 was isolated from cultivated soil cyanobacteria using a combination of centrifugal partition chromatography (CPC) and gel permeation chromatography. The solubility of Aer-865 in different solvents was evaluated using the conductor-like screening model for real solvents (COSMO-RS). The CPC separation was performed in descending mode with a biphasic solvent system composed of water-n-BuOH-acetic acid (5:4:1, v/v/v). The upper phase was used as a stationary phase, whereas the lower phase was employed as a mobile phase at a flow rate of 10 mL/min. The revolution speed and temperature of the separation column were 1700 rpm and 25 degrees C, respectively. Preparative CPC separation followed by gel permeation chromatography was performed on 50 mg of crude extract yielding Aer-865 (3.5 mg), with a purity over 95% as determined by HPLC. The chemical identity of the isolated compound was confirmed by comparing its spectroscopic data (UV, HRESI-MS, HRESI-MS/MS) with those of an authentic standard and data available in the literature.

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.

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

PubMed

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

2013-05-07

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

The potential of cloud point system as a novel two-phase partitioning system for biotransformation.

PubMed

Wang, Zhilong

2007-05-01

Although the extractive biotransformation in two-phase partitioning systems have been studied extensively, such as the water-organic solvent two-phase system, the aqueous two-phase system, the reverse micelle system, and the room temperature ionic liquid, etc., this has not yet resulted in a widespread industrial application. Based on the discussion of the main obstacles, an exploitation of a cloud point system, which has already been applied in a separation field known as a cloud point extraction, as a novel two-phase partitioning system for biotransformation, is reviewed by analysis of some topical examples. At the end of the review, the process control and downstream processing in the application of the novel two-phase partitioning system for biotransformation are also briefly discussed.

Structure and phase transitions of asphaltenes in solutions

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

Tar, M.M. de; Sheu, E.Y.; Storm, D.A.

The authors investigated the rheological properties of two vacuum resid fractions in a series of solvents. The authors measured the viscosity as a function of concentration and temperature respectively. In this study, two aspects were focused: (1) the concentration dependence of viscosity for the pentane soluble fractions in a series of n-alkane solvents for study of the particle structure, and (2) the temperature dependence of viscosity of the heptane insoluble fraction in toluene at various concentrations for the study of the phase transitions. From their results it was found that all the systems studied are Newtonian. The results for (1)more » show that the particles are approximately spherical and as the carbon number of the n-alkane solvent increases, the quality of the solvent increases, thereby increasing the particle solvation. This result is consistent with that reported in a recent paper by Ali and Saleem. Also, the particles were found to behave similarly to colloidal particles. As for (2), a glass-like transition was observed at 50% concentration (0.31 volume fraction) with glass transition temperature at about 254 K, while no structural or phase transitions were observed for concentrations below 50%.« less

Mesodomain and Protein-Associated Solvent Phases with Temperature-Tunable (200-265 K) Dynamics Surround Ethanolamine Ammonia-Lyase in Globally Polycrystalline Aqueous Solution Containing Dimethyl Sulfoxide.

PubMed

Nforneh, Benjamen; Warncke, Kurt

2017-12-14

Electron paramagnetic resonance spectroscopy of the spin probe, TEMPOL, is used to resolve solvent phases that surround the ethanolamine ammonia-lyase (EAL) protein from Salmonella typhimurium at low temperature (T) in frozen, globally polycrystalline aqueous solution and to report on the T dependence of their detectably rigid and fluid states. EAL plays a role in human gut microbiome-based disease conditions, and physicochemical studies provide insight into protein structure and mechanism, toward potential therapeutics. Temperature dependences of the rotational correlation times (τ c ; detection range, 10 -11 ≤ τ c ≤ 10 -7 s) and the corresponding weights of TEMPOL tumbling components from 200 to 265 K in the presence of EAL are measured in two frozen systems: (1) water-only and (2) 1% v/v dimethyl sulfoxide (DMSO). In the water-only condition, a protein-vicinal solvent component detectably fluidizes at 230 K and melts the surrounding ice-crystalline region with increasing T, creating a bounded, relatively high-viscosity aqueous solvent domain, up to 265 K. In the EAL, 1% v/v DMSO condition, two distinct concentric solvent phases are resolved around EAL: protein-associated domain (PAD) and mesodomain. The DMSO aqueous mesodomain fluidizes at 200 K, followed by PAD fluidization at 210 K. The interphase dynamical coupling is consistent with the spatial arrangement and significant contact areas of the phases, indicated by the experimentally determined mean volume ratio, V(mesodomain)/V(PAD)/V(protein) = 0.5:0.3:1.0. The results provide a rationale for native chemical reactions of EAL at T < 250 K and an advance toward precise control of solvent dynamics as a tunable parameter for quantifying the coupling between solvent and protein fluctuations and chemical reaction steps in EAL and other enzymes.

Method for applying a photoresist layer to a substrate having a preexisting topology

DOEpatents

Morales, Alfredo M.; Gonzales, Marcela

2004-01-20

The present invention describes a method for preventing a photoresist layer from delaminating, peeling, away from the surface of a substrate that already contains an etched three dimensional structure such as a hole or a trench. The process comprises establishing a saturated vapor phase of the solvent media used to formulate the photoresist layer, above the surface of the coated substrate as the applied photoresist is heated in order to "cure" or drive off the retained solvent constituent within the layer. By controlling the rate and manner in which solvent is removed from the photoresist layer the layer is stabilized and kept from differentially shrinking and peeling away from the substrate.

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.

Semi-Preparative Isolation and Purification of Three Tauro-Conjugated Cholic Acids from Pulvis Fellis Suis by HSCCC Coupled with ELSD Detection.

PubMed

He, Jiao; Zhang, Yongmin; Ito, Yoichiro; Sun, Wenji

2011-01-01

Coupled with evaporative light scattering detection, a high-speed counter-current chromatography (HSCCC) method was applied to the separation and purification of three tauro-conjugated cholic acids of taurochenodeoxycholic acid (TCDCA), taurohyodeoxycholic acid (THDCA) and taurohyocholic acid (THCA) from Pulvis Fellis Suis (Pig gallbladder bile) for the first time. The two-phase solvent system composed of chloroform-methanol-water-acetic acid (4:4:2:0.3, v/v/v/v) was selected for the one-step separation where the lower phase was used as the mobile phase in the head to tail elution mode. The revolution speed of the separation column, flow rate of the mobile phase and separation temperature were 800 rpm, 1.5 ml/min and 25°C respectively. From 100 mg of the crude extract, 10.2 mg of TCDCA, 11.8 mg of THDCA and 5.3 mg of THCA were obtained with the purity of 94.6%, 96.5% and 95.4%, respectively. in one step separation The HSCCC fractions were analyzed by high-performance liquid chromatography (HPLC) and the structures of the three tauro-conjugated cholic acids were identified by ESI-MS, (1)H NMR and (13)C NMR.

Modified two-step emulsion solvent evaporation technique for fabricating biodegradable rod-shaped particles in the submicron size range.

PubMed

Safari, Hanieh; Adili, Reheman; Holinstat, Michael; Eniola-Adefeso, Omolola

2018-05-15

Though the emulsion solvent evaporation (ESE) technique has been previously modified to produce rod-shaped particles, it cannot generate small-sized rods for drug delivery applications due to the inherent coupling and contradicting requirements for the formation versus stretching of droplets. The separation of the droplet formation from the stretching step should enable the creation of submicron droplets that are then stretched in the second stage by manipulation of the system viscosity along with the surface-active molecule and oil-phase solvent. A two-step ESE protocol is evaluated where oil droplets are formed at low viscosity followed by a step increase in the aqueous phase viscosity to stretch droplets. Different surface-active molecules and oil phase solvents were evaluated to optimize the yield of biodegradable PLGA rods. Rods were assessed for drug loading via an imaging agent and vascular-targeted delivery application via blood flow adhesion assays. The two-step ESE method generated PLGA rods with major and minor axis down to 3.2 µm and 700 nm, respectively. Chloroform and sodium metaphosphate was the optimal solvent and surface-active molecule, respectively, for submicron rod fabrication. Rods demonstrated faster release of Nile Red compared to spheres and successfully targeted an inflamed endothelium under shear flow in vitro and in vivo. Copyright © 2018 Elsevier Inc. All rights reserved.

Deep eutectic solvent based gas-assisted dispersive liquid-phase microextraction combined with gas chromatography and flame ionization detection for the determination of some pesticide residues in fruit and vegetable samples.

PubMed

Farajzadeh, Mir Ali; Sattari Dabbagh, Masoumeh; Yadeghari, Adeleh

2017-05-01

In this study, a gas-assisted dispersive liquid-phase microextraction method using a deep eutectic solvent as the extraction solvent combined with gas chromatography and flame ionization detection was developed for the extraction and determination of some pesticide residues in vegetable and fruit juice samples. In this method, choline chloride and 4-chlorophenol at a molar ratio of 1:2 were mixed. By heating and vortexing, a clear, water-immiscible, and homogeneous liquid was formed. The obtained deep eutectic solvent was added to an aqueous solution of the analytes in a conical test tube. Air was bubbled into the aqueous solution and a cloudy solution was obtained. During this step, the analytes were extracted into the fine droplets of the extraction solvent. After centrifugation, an aliquot of the settled phase was injected into the separation system. Under the optimum extraction conditions, enrichment factors, and extraction recoveries were obtained in the ranges of 247-355 and 49-71%, respectively. The obtained values for the limits of detection and quantification were in the ranges of 0.24-1.4 and 0.71-4.2 μg/L, respectively. The proposed method is simple, fast, efficient, and inexpensive. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

PREPARATIVE ISOLATION AND PURIFICATION OF THREE GLYCINE-CONJUGATED CHOLIC ACIDS FROM PULVIS FELLIS SUIS BY HIGH-SPEED COUNTERCURRENT CHROMATOGRAPHY COUPLED WITH ELSD DETECTION.

PubMed

He, Jiao; Li, Jing; Sun, Wenji; Zhang, Tianyou; Ito, Yoichiro

2012-01-01

Coupled with evaporative light scattering detection, a high-speed counter-current chromatography (HSCCC) method was developed for preparative isolation and purification of three glycine-conjugated cholic acids, glycochenodeoxycholic acid (GCDCA), glycohyodeoxycholic acid (GHDCA) and glycohyocholic acid (GHCA) from Pulvis Fellis Suis (Pig gallbladder bile) for the first time. The separation was performed with a two-phase solvent system consisted of chloroform-methanol-water-acetic acid (65:30:10:1.5, v/v/v/v) by eluting the lower phase in the head-to-tail elution mode. The revolution speed of the separation column, flow rate of the mobile phase and separation temperature were 800 rpm, 2 ml/min and 25 °C, respectively. In a single operation, 33 mg of GCDCA, 38 mg of GHDCA and 23 mg of GHCA were obtained from 200 mg of crude extract with the purity of 95.65%, 96.72% and 96.63%, respectively, in one step separation. The HSCCC fractions were analyzed by high-performance liquid chromatography (HPLC) and the structures of the three glycine-conjugated cholic acids were identified by ESI-MS, (1)H NMR and (13)C NMR.

PREPARATIVE ISOLATION AND PURIFICATION OF THREE GLYCINE-CONJUGATED CHOLIC ACIDS FROM PULVIS FELLIS SUIS BY HIGH-SPEED COUNTERCURRENT CHROMATOGRAPHY COUPLED WITH ELSD DETECTION

PubMed Central

He, Jiao; Li, Jing; Sun, Wenji; Zhang, Tianyou; Ito, Yoichiro

2011-01-01

Coupled with evaporative light scattering detection, a high-speed counter-current chromatography (HSCCC) method was developed for preparative isolation and purification of three glycine-conjugated cholic acids, glycochenodeoxycholic acid (GCDCA), glycohyodeoxycholic acid (GHDCA) and glycohyocholic acid (GHCA) from Pulvis Fellis Suis (Pig gallbladder bile) for the first time. The separation was performed with a two-phase solvent system consisted of chloroform-methanol-water-acetic acid (65:30:10:1.5, v/v/v/v) by eluting the lower phase in the head-to-tail elution mode. The revolution speed of the separation column, flow rate of the mobile phase and separation temperature were 800 rpm, 2 ml/min and 25 °C, respectively. In a single operation, 33 mg of GCDCA, 38 mg of GHDCA and 23 mg of GHCA were obtained from 200 mg of crude extract with the purity of 95.65%, 96.72% and 96.63%, respectively, in one step separation. The HSCCC fractions were analyzed by high-performance liquid chromatography (HPLC) and the structures of the three glycine-conjugated cholic acids were identified by ESI-MS, 1H NMR and 13C NMR. PMID:23008527

Three-Dimensional Morphology Control Yielding Enhanced Hole Mobility in Air-Processed Organic Photovoltaics: Demonstration with Grazing-Incidence Wide-Angle X-ray Scattering

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

Moore, Levi M. J.; Bhattacharya, Mithun; Wu, Qi

Polymer organic photovoltaic (OPV) device performance is defined by the three-dimensional morphology of the phase-separated domains in the active layer. Here, we determine the evolution of morphology through different stages of tailored solvent vapor and thermal annealing techniques in air-processed poly(3-hexylthiophene-2,5-diyl)/phenyl-C61-butyric acid methyl ester-based OPV blends. A comparative evaluation of the effect of solvent type used for vapor annealing was performed using grazing-incidence wide-angle X-ray scattering, atomic force microscopy, and UV–vis spectroscopy to probe the active-layer morphology. A nonhalogenated orthogonal solvent was found to impart controlled morphological features within the exciton diffusion length scales, enhanced absorbance, greater crystallinity, increased paracrystallinemore » disorder, and improved charge-carrier mobility. Low-boiling, fast-diffusing isopropanol allowed the greatest control over the nanoscale structure of the solvents evaluated and yielded a cocontinuous morphology with narrowed domains and enhanced paths for the charge carrier to reach the anode.« less

On the nature of solvatochromic effect: The riboflavin absorption spectrum as a case study

NASA Astrophysics Data System (ADS)

Daidone, Isabella; Amadei, Andrea; Aschi, Massimiliano; Zanetti-Polzi, Laura

2018-03-01

We present here the calculation of the absorption spectrum of riboflavin in acetonitrile and dimethyl sulfoxide using a hybrid quantum/classical approach, namely the perturbed matrix method, based on quantum mechanical calculations and molecular dynamics simulations. The calculated spectra are compared to the absorption spectrum of riboflavin previously calculated in water and to the experimental spectra obtained in all three solvents. The experimentally observed variations in the absorption spectra upon change of the solvent environment are well reproduced by the calculated spectra. In addition, the nature of the excited states of riboflavin interacting with different solvents is investigated, showing that environment effects determine a recombination of the gas-phase electronic states and that such a recombination is strongly affected by the polarity of the solvent inducing significant changes in the absorption spectra.

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.

An absorbing microwave micro-solid-phase extraction device used in non-polar solvent microwave-assisted extraction for the determination of organophosphorus pesticides.

PubMed

Wang, Ziming; Zhao, Xin; Xu, Xu; Wu, Lijie; Su, Rui; Zhao, Yajing; Jiang, Chengfei; Zhang, Hanqi; Ma, Qiang; Lu, Chunmei; Dong, Deming

2013-01-14

A single-step extraction-cleanup method, including microwave-assisted extraction (MAE) and micro-solid-phase extraction (μ-SPE), was developed for the extraction of ten organophosphorus pesticides in vegetable and fruit samples. Without adding any polar solvent, only one kind of non-polar solvent (hexane) was used as extraction solvent in the whole extraction step. Absorbing microwave μ-SPE device, was prepared by packing activated carbon with microporous polypropylene membrane envelope, and used as not only the sorbent in μ-SPE, but also the microwave absorption medium. Some experimental parameters effecting on extraction efficiency was investigated and optimized. 1.0 g of sample, 8 mL of hexane and three absorbing microwave μ-SPE devices were added in the microwave extraction vessel, the extraction was carried out under 400 W irradiation power at 60°C for 10 min. The extracts obtained by MAE-μ-SPE were directly analyzed by GC-MS without any clean-up process. The recoveries were in the range of 93.5-104.6%, and the relative standard deviations were lower than 8.7%. Copyright © 2012 Elsevier B.V. All rights reserved.

Morphology of molecular soy protein fractions in binary composite gels.

PubMed

Kasapis, Stefan; Tay, Sok Li

2009-08-04

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

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.

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.

The docking of chiral analytes on proline-based chiral stationary phases: A molecular dynamics study of selectivity.

PubMed

Ashtari, M; Cann, N M

2015-08-28

Molecular dynamics simulations are employed to examine the selectivity of four proline-based chiral stationary phases in two solvent environments, a relatively apolar n-hexane/2-propanol solvent and a polar water/methanol solvent. The four chiral surfaces are based on a BOC-terminated diproline, a TMA-terminated diproline, a TMA-terminated triproline and a TMA-terminated hexaproline. This range of chiral selectors allows an analysis of the impact of oligomer length and terminal group on selectivity while the two solvent environments indicate the impact of solvent hydrogen bonding and polarity. The selector-analyte interactions are examined for six closely related analytes that each have an aromatic moiety, a hydrogen, and an alcohol group directly bonded to the stereocenter. The analytes differ in the nature of the aromatic group (phenyl or anthracyl), in the attachment point (to the central ring or a side ring in the anthracyl), and in the fourth group bonded to the carbon (CH3, CF3, or C2H5). For each of the 48 solvent+selector+analyte systems, selectivity factors are calculated and, when possible, compared to experiment. The docking mode for these proline-based selectors is analyzed. Copyright © 2015 Elsevier B.V. All rights reserved.

Poly-proline-based chiral stationary phases: a molecular dynamics study of triproline, tetraproline, pentaproline and hexaproline interfaces.

PubMed

Ashtari, M; Cann, N M

2012-11-23

Poly-proline chains and derivatives have been recently examined as the basis for new chiral stationary phases in high performance liquid chromatography. The selectivity of poly-proline has been measured for peptides with up to ten proline units. In this article, we employ molecular dynamics simulations to examine the interfacial structure and solvation of surface-bound poly-proline chiral selectors. Specifically, we study the interfacial structure of trimethylacetyl-terminated poly-proline chains with three-to-six prolines. The surface includes silanol groups and end-caps, to better capture the characteristics of the stationary phase, and the solvent is either a polar water/methanol or a relatively apolar n-hexane/2-propanol mixture. We begin with a comprehensive ab initio study of the conformers, their energies, and an assessment of conformer flexibility. Force fields have been developed for each poly-proline selector. Molecular dynamics simulations are employed to study the preferred backbone conformations and solvent hydrogen bonding for different poly-proline/solvent interfaces. For triproline, the effect of two different terminal groups, trimethylacetyl and t-butyl carbamate are compared. Copyright © 2012 Elsevier B.V. All rights reserved.

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.

Preparative isolation and purification of senkyunolide-I, senkyunolide-H and ferulic acid from Rhizoma Chuanxiong using counter-current chromatography.

PubMed

Wei, Yun; Hu, Jia; Li, Hao; Liu, Jiangang

2011-12-01

Three active compounds, senkyunolide-I, senkyunolide-H and ferulic acid (FA), were successfully isolated and purified from the extracts of Rhizoma Chuanxiong by counter-current chromatography (CCC). Based on the principle of the partition coefficient values (k) for target compounds and the separation factor (α) between target compounds, the two-phase solvent system that contains n-hexane-ethyl acetate-methanol-water at an optimized volume ratio of 3:7:4:6 v/v was selected for the CCC separation, and the lower phase was employed as the mobile phase in the head-to-tail elution mode. In a single run, 400 mg of the crude extract yielded pure senkyunolide-I (6.4 mg), senkyunolide-H (1.7 mg) and FA (4.4 mg) with the purities of 98, 93 and 99%, respectively. The CCC fractions were analyzed by high-performance liquid chromatography, and the structures of the three active compounds were identified by MS and (1)H NMR. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Isolation and purification of series bioactive components from Hypericum perforatum L. by counter-current chromatography.

PubMed

Cao, Xueli; Wang, Qiaoe; Li, Yan; Bai, Ge; Ren, Hong; Xu, Chunming; Ito, Yoichiro

2011-03-01

Counter-current chromatography (CCC) combined with pre-separation by ultrasonic solvent extraction was successively used for the separation of series bioactive compounds from the crude extract of Hypericum perforatum L. The petroleum ether extract was separated by the solvent system of n-heptane-methanol-acetonitrile (1.5:0.5:0.5, v/v) and n-heptane-methanol (1.5:1, v/v) in gradient elution, yielding a phloroglucinol compound, hyperforin with HPLC purity over 98%. The ethyl acetate extract was separated by using the solvent system composed of hexane-ethyl acetate-methanol-water (1:1:1:1 and 1:3:1:3, v/v) in gradient through both reverse phase and normal phase elution mode, yielding a naphthodianthrone compound, hypericin with HPLC purity about 95%. The n-butanol extract was separated with the solvent system composed of n-butanol-ethyl acetate-water (1:4:5 and 1.5:3.5:5, v/v) in elution and back-extrusion mode, yielding two of flavones, rutin and hyperoside, with HPLC purity over 95%. HPLC-MS, reference sample and UV spectrum were selectively used in separation to search for target compounds from HPLC-DAD profiles of different sub-extracts. The structures of isolated compounds were further identified by ESI-MS, ¹HNMR and ¹³CNMR. Copyright © 2011 Elsevier B.V. All rights reserved.

Isolation and purification of series bioactive components from Hypericum Perforatum L. by high-speed counter-current chromatography

PubMed Central

Cao, Xueli; Wang, Qiaoe; Li, Yan; Bai, Ge; Ren, Hong; Ito, Yiochiro

2011-01-01

High-speed counter-current chromatography (HSCCC) combined with pre-separation by ultrasonic solvent extraction was successively used for the separation of series bioactive compounds from the crude extract of Hypericum perforatum L. The petroleum ether extract was separated by the solvent system of n-heptane-methanol-acetonitrile (1.5:0.5:0.5, v/v) and n-heptane-methanol (1.5:1, v/v) in gradient elution, yielding a phloroglucinol compound, hyperforin with HPLC purity over 98%. The ethyl acetate extract was separated by using the solvent system composed of hexane-ethyl acetate-methanol-water (1:1:1:1 and 1:3:1:3, v/v) in gradient through both reverse phase and normal phase elution mode, yielding a naphthodianthrone compound, hypericin with HPLC purity about 95%. The n-butanol extract was separated with the solvent system composed of n-butanol-ethyl acetate–water (1:4:5 and 1.5:3.5:5, v/v) in elution and back-extrusion mode, yielding two of flavones, rutin and hyperoside, with HPLC purity over 95%. HPLC-MS, reference sample and UV spectrum were selectively used in separation to search for target compounds from HPLC-DAD profiles of different sub-extracts. The structures of isolated compounds were further identified by ESI-MS, 1HNMR and 13CNMR. PMID:21306961

Mesophase and size manipulation of itraconazole liquid crystalline nanoparticles produced via quasi nanoemulsion precipitation.

PubMed

Mugheirbi, Naila A; Tajber, Lidia

2015-10-01

The fabrication of drug nanoparticles (NPs) with process-mediated tunable properties and performances continues to grow rapidly during the last decades. This study investigates the synthesis and phase tuning of nanoparticulate itraconazole (ITR) mesophases using quasi nanoemulsion precipitation from acetone/water systems to seek out an alternative pathway to the nucleation-based NP formation. ITR liquid crystalline (LC) phases were formed and nematic-smectic mesomorphism was achieved via controlling solvent:antisolvent temperature difference (ΔTS:AS). The use of ΔTS:AS=49.5°C was associated with a nematic assembly, while intercalated smectic A layering was observed at ΔTS:AS=0°C, with both phases confined in the nanospheres at room temperature. The quasi emulsion system has not been investigated at the nanoscale to date and in contrary to the microscale, quasi nanoemulsion was observed over the solvent:antisolvent viscosity ratios of 1:7-1:1.4. Poly(acrylic acid) in the solvent phase exhibited a concentration dependent interaction when ITR formed NPs. This nanodroplet-based approach enabled the preparation of a stable ITR nanodispersion using Poloxamer 407 at 80°C, which was unachievable before using precipitation via nucleation. Findings of this work lay groundwork in terms of rationalised molecular assembly as a tool in designing pharmaceutical LC NPs with tailored properties. Copyright © 2015 Elsevier B.V. All rights reserved.

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

Pyrene fate affected by humic acid amendment in soil slurry systems.

PubMed

Liang, Yanna; Sorensen, Darwin L; McLean, Joan E; Sims, Ronald C

2008-09-10

Humic acid (HA) has been found to affect the solubility, mineralization, and bound residue formation of polycyclic aromatic hydrocarbons (PAHs). However, most of the studies on the interaction between HA and PAH concentrated on one or two of the three phases. Few studies have provided a simple protocol to demonstrate the overall effects of HA on PAH distribution in soil systems for all three phases. In this study, three doses of standard Elliott soil HA (ESHA), 15, 187.5, and 1,875 mug ESHA/g soil slurry, were amended to soil slurry systems. 14C-pyrene was added to the systems along with non-radiolabeled pyrene; 14C and 14CO2 were monitored for each system for a period of 120 days. The highest amendment dose significantly increased the 14C fraction in the aqueous phase within 24 h, but not after that time. Pyrene mineralization was significantly inhibited by the highest dose over the 120-day study. While organic solvent extractable 14C decreased with time in all systems, non-extractable or bound 14C was significantly enhanced with the highest dose of ESHA addition. Amendment of the highest dose of ESHA to pyrene contaminated soil was observed to have two major functions. The first was to mitigate CO2 production significantly by reducing 14CO2 from 14C pyrene mineralization. The second was to significantly increase stable bound 14C formation, which may serve as a remediation end point. Overall, this study demonstrated a practical approach for decontamination of PAH contaminated soil. This approach may be applicable to other organic contaminated environments where active bioremediation is taking place.

Preparative isolation and purification of three sesquiterpenoid lactones from Eupatorium lindleyanum DC. by high-speed counter-current chromatography.

PubMed

Yan, Guilong; Ji, Lilian; Luo, Yuming; Hu, Yonghong

2012-07-27

A high-speed counter-current chromatography (HSCCC) method was established for the preparative separation of three sesquiterpenoid lactones from Eupatorium lindleyanum DC. The two-phase solvent system composed of n-hexane-ethyl acetate-methanol-water (1:4:2:3, v/v/v/v) was selected. From 540 mg of the n-butanol fraction of Eupatorium lindleyanum DC., 10.8 mg of 3β-hydroxy-8β-[4'-hydroxytigloyloxy]-costunolide, 17.9 mg of eupalinolide A and 19.3 mg of eupalinolide B were obtained in a one-step HSCCC separation, with purities of 91.8%, 97.9% and 97.1%, respectively, as determined by HPLC. Their structures were further identified by ESI-MS and ¹H-NMR.

Phase behavior of the mixtures of poly(oxyethylene) (10) stearyl ether (Brij-76), 1-butanol, isooctane, and mixed polar solvents II. Water and ethylene glycol (EG) or tetraethylene glycol (TEG).

PubMed

Nandy, Debdurlav; Mitra, Rajib K; Paul, Bidyut K

2007-06-01

The phase diagrams of the pseudo-quaternary systems poly(oxyethylene) (10) stearyl ether (Brij-76)/1-butanol/isooctane/water (with equal amounts of oil and water in the presence of two nonaqueous polar solvents (NPS), ethylene glycol (EG), and tetraethylene glycol (TEG)), have been constructed at 30 degrees C. Regular fish-tail diagrams were obtained up to psi (weight fraction of EG or TEG in the mixture of polar solvents) equal to 0.5, confirming the establishment of hydrophile-lipophile balance (HLB) of the systems. The maximum solubilization capacity passed through a minimum at psi=0.2. No HLB was obtained at higher psi. The usual fish-tail diagrams were also obtained in temperature-induced phase mapping at fixed W(1) (weight fraction of 1-butanol in total amphiphile). Solubilization capacity and HLB temperature (T(HLB)) decreased with increasing psi at a fixed W(1), the effect being more pronounced for TEG than EG. A correlation between HLB temperature (T(HLB)) and HLB number (N(HLB)) of mixed amphiphiles (Brij-76+Bu) in pseudo-quaternary systems (in the presence of water and partial substitution of water with both NPS) has been established. The novelty of the work with respect to possible applications has been discussed.

Design of a coil satellite centrifuge and its performance on counter-current chromatographic separation of 4-methylumbelliferyl sugar derivatives with polar organic-aqueous two-phase solvent systems.

PubMed

Shinomiya, Kazufusa; Tokura, Koji; Kimura, Emiru; Takai, Midori; Harikai, Naoki; Yoshida, Kazunori; Yanagidaira, Kazuhiro; Ito, Yoichiro

2015-05-01

A new high-speed counter-current chromatograph, named coil satellite centrifuge (CSC), was designed and fabricated in our laboratory. The CSC apparatus produces the satellite motion such that the coiled column simultaneously rotates around the sun axis (the angular velocity, ω1), the planet axis (ω2) and the satellite axis (the central axis of the column) (ω3). In order to achieve this triplicate rotary motion without twisting of the flow tube, the rotation of each axis was determined by the following formula: ω1=ω2+ω3. This relation enabled to lay out the flow tube without twisting by the simultaneous rotation of three axes. The flow tube was introduced from the bottom side of the apparatus into the sun axis of the first rotary frame reaching the upper side of the planet axis and connected to the column in the satellite axis. The performance of the apparatus was examined on separation of 4-methylumbelliferyl (MU) sugar derivatives as test samples with organic-aqueous two-phase solvent systems composed of ethyl acetate/1-butanol/water (3:2:5, v/v) for lower phase mobile and (1:4:5, v/v) for upper phase mobile. With lower phase mobile, five 4-MU sugar derivatives including β-D-cellobioside (Cel), β-D-glucopyranoside, α-D-mannopyranoside, β-D-fucopyranoside and α-L-fucopyranoside (α-L-Fuc) were separated with the combined rotation around each axis at counterclockwise (CCW) (ω1) - CCW (ω2) - CCW (ω3) by the flow tube distribution. With upper phase mobile, three 4-MU sugar derivatives including α-L-Fuc, β-D-galactopyranoside and Cel were separated with the combined rotation around each axis at clockwise (CW) (ω1) - CW (ω2) - CW (ω3) by the flow tube distribution. A series of experiments on peak resolution and stationary phase retention revealed that better partition efficiencies were obtained at the flow rate of 0.5 mL/min (column 1) and 0.8 mL/min (column 2) for lower phase mobile and 0.2 mL/min (column 1) and 0.4 mL/min (column 2) for upper phase mobile when using the left-handed multilayer coil (total capacity: 57.0 mL for column 1 and 75.0 mL for column 2) under the rotation speeds of approximately ω1=300 rpm, ω2=150 rpm and ω3=150 rpm. Copyright © 2015 Elsevier B.V. All rights reserved.

Effect of dynamic surface polarization on the oxidative stability of solvents in nonaqueous Li-O 2 batteries

NASA Astrophysics Data System (ADS)

Khetan, Abhishek; Pitsch, Heinz; Viswanathan, Venkatasubramanian

2017-09-01

Polarization-induced renormalization of the frontier energy levels of interacting molecules and surfaces can cause significant shifts in the excitation and transport behavior of electrons. This phenomenon is crucial in determining the oxidative stability of nonaqueous electrolytes in high-energy density electrochemical systems such as the Li-O2 battery. On the basis of partially self-consistent first-principles Sc G W0 calculations, we systematically study how the electronic energy levels of four commonly used solvent molecules, namely, dimethylsulfoxide (DMSO), dimethoxyethane (DME), tetrahydrofuran (THF), and acetonitrile (ACN), renormalize when physisorbed on the different stable surfaces of Li2O2 , the main discharge product. Using band level alignment arguments, we propose that the difference between the solvent's highest occupied molecular orbital (HOMO) level and the surface's valence-band maximum (VBM) is a refined metric of oxidative stability. This metric and a previously used descriptor, solvent's gas phase HOMO level, agree quite well for physisorbed cases on pristine surfaces where ACN is oxidatively most stable followed by DME, THF, and DMSO. However, this effect is intrinsically linked to the surface chemistry of the solvent's interaction with the surface states and defects, and depends strongly on their nature. We conclusively show that the propensity of solvent molecules to oxidize will be significantly higher on Li2O2 surfaces with defects as compared to pristine surfaces. This suggests that the oxidative stability of a solvent is dynamic and is a strong function of surface electronic properties. Thus, while gas phase HOMO levels could be used for preliminary solvent candidate screening, a more refined picture of solvent stability requires mapping out the solvent stability as a function of the state of the surface under operating conditions.

Cesium and strontium extraction using a mixed extractant solvent including crown ether and calixarene extractants

DOEpatents

Meikrantz, David H.; Todd, Terry A.; Riddle, Catherine L.; Law, Jack D.; Peterman, Dean R.; Mincher, Bruce J.; McGrath, Christopher A.; Baker, John D.

2007-11-06

A mixed extractant solvent including calix[4]arene-bis-(tert-octylbenzo)-crown-6 ("BOBCalixC6"), 4',4',(5')-di-(t-butyldicyclo-hexano)-18-crown-6 ("DtBu18C6"), and at least one modifier dissolved in a diluent. The mixed extractant solvent may be used to remove cesium and strontium from an acidic solution. The DtBu18C6 may be present from approximately 0.01 M to approximately 0.4M, such as from approximately 0.086 M to approximately 0.108 M. The modifier may be 1-(2,2,3,3-tetrafluoropropoxy)-3-(4-sec-butylphenoxy)-2-propanol ("Cs-7SB") and may be present from approximately 0.01M to approximately 0.8M. In one embodiment, the mixed extractant solvent includes approximately 0.15M DtBu18C6, approximately 0.007M BOBCalixC6, and approximately 0.75M Cs-7SB modifier dissolved in an isoparaffinic hydrocarbon diluent. The mixed extractant solvent may form an organic phase in an extraction system that also includes an aqueous phase. Methods of extracting cesium and strontium as well as strontium alone are also disclosed.

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

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.

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.

COMPARISON OF TWO DIFFERENT SOLID PHASE EXTRACTION/LARGE VOLUME INJECTION PROCEDURES FOR METHOD 8270

EPA Science Inventory

Two solid phase (SPE) and one traditional continuous liquid-liquid extraction method are compared for analysis of Method 8270 SVOCs. Productivity parameters include data quality, sample volume, analysis time and solvent waste.

One SPE system, unique in the U.S., uses aut...

Semiautomated solid-phase extraction manifold with a solvent-level sensor.

PubMed

Orlando, R M; Rath, S; Rohwedder, J J R

2013-11-15

A semiautomated solid-phase extraction manifold for multiple extractions is presented. The manifold utilizes commercial solid-phase syringe cartridges and automatically introduces and elutes all the solvents during the extraction, reducing the typical workload and stress of the analyst. The manifold consists of a peristaltic pump with solenoid valves in a flow circuit that contains transmissive photomicrosensors. The photomicrosensors were used to control the solvent dispenser and the solvent level inside the cartridge. As solvent-level sensors, the photomicrosensors determined the exact time the solvent reached the top frit to avoid sorbent drying and accurately perform the solvent exchange. The repeatability of the manifold to introduce a particular volume of solvent into the cartridges was measured, and the precisions were between 0.05 and 2.89% (RSD). To evaluate the manifold, the amount of two fluoroquinolones in a fortified blank milk sample was determined. The results of the intra- and inter-day precision of multiple extractions from the fortified milk samples resulted in precisions better than 9.0% (RSD) and confirmed that the arrangement of the semiautomated manifold could adequately be used in solid-phase extraction with commercial cartridges. Copyright © 2013 Elsevier B.V. All rights reserved.

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.

Micro-Raman Technology to Interrogate Two-Phase Extraction on a Microfluidic Device.

PubMed

Nelson, Gilbert L; Asmussen, Susan E; Lines, Amanda M; Casella, Amanda J; Bottenus, Danny R; Clark, Sue B; Bryan, Samuel A

2018-05-21

Microfluidic devices provide ideal environments to study solvent extraction. When droplets form and generate plug flow down the microfluidic channel, the device acts as a microreactor in which the kinetics of chemical reactions and interfacial transfer can be examined. Here, we present a methodology that combines chemometric analysis with online micro-Raman spectroscopy to monitor biphasic extractions within a microfluidic device. Among the many benefits of microreactors is the ability to maintain small sample volumes, which is especially important when studying solvent extraction in harsh environments, such as in separations related to the nuclear fuel cycle. In solvent extraction, the efficiency of the process depends on complex formation and rates of transfer in biphasic systems. Thus, it is important to understand the kinetic parameters in an extraction system to maintain a high efficiency and effectivity of the process. This monitoring provided concentration measurements in both organic and aqueous plugs as they were pumped through the microfluidic channel. The biphasic system studied was comprised of HNO 3 as the aqueous phase and 30% (v/v) tributyl phosphate in n-dodecane comprised the organic phase, which simulated the plutonium uranium reduction extraction (PUREX) process. Using pre-equilibrated solutions (post extraction), the validity of the technique and methodology is illustrated. Following this validation, solutions that were not equilibrated were examined and the kinetics of interfacial mass transfer within the biphasic system were established. Kinetic results of extraction were compared to kinetics already determined on a macro scale to prove the efficacy of the technique.

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

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.

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.

Solvent Effect on Morphology and Optical Properties of Poly(3-hexylthiophene):TIPS-Pentacene Blends

NASA Astrophysics Data System (ADS)

Ozório, Maíza Silva; Camacho, Sabrina Alessio; Cordeiro, Neusmar Junior Artico; Duarte, José Leonil; Alves, Neri

2018-02-01

Optical, electrical, and morphological properties of poly(3-hexylthiophene):6,13-bis(triisopropylsilylethynyl) (TIPS)-pentacene (P3HT:TP) blend films, in the proportion of 1:1 (w/w), have been investigated using chloroform, toluene, or trichlorobenzene as solvent. The main morphological feature was formation of aggregates that tended to segregate vertically, exhibiting characteristics that were strongly influenced by the type of solvent applied. The phase segregation of TP observed for the P3HT:TP blend film obtained using chloroform, the most volatile of the investigated solvents, can be explained based on the Marangoni effect and the Flory-Huggins model. The TP molecules induce better organization of P3HT, as evidenced by the ultraviolet-visible (UV-Vis) absorption spectra. Photoluminescence (PL) measurements revealed quenching and an increase in the lifetime of the carriers. The PL measurements also showed that the exciton dissociation was dependent on the characteristics of the surface on which the film was deposited. P3HT:TP blend film prepared using trichlorobenzene showed the best morphology with moderate phase segregation and better P3HT ordering. The output current from organic field-effect transistors (OFETs) with blend film prepared using trichlorobenzene was three times (3×) larger than when using the other solvents, with carrier mobility of 5.0 × 10-3 cm2 V-1 s-1.

AMINE EXTRACTION OF PLUTONIUM FROM NITRIC ACID SOLUTIONS LOADING AND STRIPPING EXPERIMENTS

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

Wilson, A.S.

1961-01-19

Information is presented on a suitable amine processing system for plutonium nitrate. Experiments with concentrated plutonium nitrate solutions show that trilaurylamine (TLA) - xylene solvent systems did not form a second organic phase. Experiments are also reported with tri-noctylamine (TnOA)-xylene and TLA-Amsco - octyl alcohol. Two organic phases appear in both these systems at high plutonium nitrate concentrations. Data are tabulated from loading and stripping experiments. (J.R.D.)

Application of liquid-liquid interactions with single-walled carbon nanotubes

NASA Astrophysics Data System (ADS)

Wang, Randy Kai-Wei

This study covers three important research topics related to the application of liquid-liquid interaction with single-walled carbon nanotubes (SWNTs). The first topic describes the removal of SWNT bundles from liquid suspensions of nanotubes. The key to this work includes the use of liquid-liquid interfaces to trap the SWNT bundles due to the free energy change of the system during the process. SWNTs pack into crystalline ropes that form bundles due to strong van der Waals attraction. Bundling diminishes mechanical and electronic properties because it could interrupt the electronic structure of the nanotubes. Also, the electronic devices based on as-grown nanotubes, which contains a mixture of individual nanotubes and nanotube bundles, make the electrical response unpredictable. We developed a new simple process to remove bundles by liquid-liquid interaction. SWNTs bundles are trapped at the interface because bundles stabilize the emulsions. Eliminating the use of ultracentrifugation to remove SWNT bundles enables large-scale production with reduced production costs and time savings. The second topic presented the swelling effect of the surfactant layer surrounding SWNTs with nonpolar solvents. Solvatochromic shifts in the absorbance and fluorescence spectra are observed when surfactant-stabilized aqueous SWNT suspensions are mixed with immiscible organic solvents. When aqueous surfactant-suspended SWNTs are mixed with certain solvents, the spectra closely match the peaks for SWNTs dispersed in only that solvent. These spectral changes suggest the hydrophobic region of the micelle surrounding SWNTs swells with the organic solvent when mixed. The solvatochromic shifts of the aqueous SWNT suspensions are reversible once the solvent evaporates. However, some surfactant-solvent systems show permanent changes to the fluorescence emission intensity after exposure to the organic solvent. The intensity of some large diameter SWNT (n, m) types increase by more than 175%. These differences are attributed to surfactant reorganization, which can improve nanotube coverage, resulting in decreased exposure to quenching mechanisms from the aqueous phase. The third topic describes the further study of the solvatochromism of the SWNTs. Since SWNTs are encapsulated with microenvironments of nonpolar solvents, it provides a new method to measure the photophysical properties of nanotubes in environments with known properties. Fluorescence and absorbance spectra of SWNTs show solvatochromic shifts in 16 nonpolar solvents, which are proportional to the solvent induction polarization. The photophysical properties of SWNTs were used to determine the relationship between the longitudinal polarizability and other nanotube properties, alpha11,|| ∝ 1/(R2E11 3). (Full text of this dissertation may be available via the University of Florida Libraries web site. Please check http://www.uflib.ufl.edu/etd.html)

Dilute and Semidilute Solutions of a Nonionic, Rigid, Water-soluble Polymer

NASA Astrophysics Data System (ADS)

Russo, Paul; Huberty, Wayne; Zhang, Donghui; Water-Soluble Rodlike Polymer Team Collaboration

2014-03-01

The solution physics of random polymer chains was established largely on the behavior of commercial polymers such as polystyrene for organic solvents or nonionic poly(ethyleneoxide) for aqueous solvents. Not only are these materials widely available for industrial use, they can be synthesized to be essentially monodisperse. When it comes to stiff polymers, good choices are few and less prone to be used in industrial applications. Much was learned from polypeptides such as poly(benzylglutamate) or poly(stearylglutamate) in polar organic solvents and nonpolar organic solvents, respectively, but aqueous systems generally require charge. Poly(Nɛ-2-[2-(2-Methoxyethoxy) ethoxy]acetyl-L-Lysine) a.k.a. PEGL was pioneered by Deming and coworkers. In principle, PEGL provides a convenient platform from which to study stiff polymer behavior--phase relations, dynamics, liquid crystal formation and gelation--all with good molecular weight control and uniformity and without electrical charge. Still, a large gap in knowledge exists between PEGL and traditional rodlike polymer systems. To narrow this gap, dynamic and static scattering, circular dichroism, and viscosity measurements have been made in dilute and semidilute solutions as necessary preliminaries for lyotropic liquid crystalline and gel phases. Supported by NSF DMR 1306262. Department of Chemistry and Macromolecular Studies Group. Current address: Georgia Institute of Technology, School of Materials Science and Engineering.

Development of the Next-Generation Caustic-Side Solvent Extraction (NG-CSSX) Process for Cesium Removal from High-Level Tank Waste

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

Moyer, Bruce A; Bonnesen, Peter V; Delmau, Laetitia Helene

2011-01-01

This paper describes the chemical performance of the Next-Generation Caustic-Side Solvent Extraction (NG-CSSX) process in its current state of development for removal of cesium from the alkaline high-level tank wastes at the Savannah River Site (SRS) in the US Department of Energy (USDOE) complex. Overall, motivation for seeking a major enhancement in performance for the currently deployed CSSX process stems from needs for accelerating the cleanup schedule and reducing the cost of salt-waste disposition. The primary target of the NG-CSSX development campaign in the past year has been to formulate a solvent system and to design a corresponding flowsheet thatmore » boosts the performance of the SRS Modular CSSX Unit (MCU) from a current minimum decontamination factor of 12 to 40,000. The chemical approach entails use of a more soluble calixarene-crown ether, called MaxCalix, allowing the attainment of much higher cesium distribution ratios (DCs) on extraction. Concurrently decreasing the Cs-7SB modifier concentration is anticipated to promote better hydraulics. A new stripping chemistry has been devised using a vitrification-friendly aqueous boric acid strip solution and a guanidine suppressor in the solvent, resulting in sharply decreased DCs on stripping. Results are reported herein on solvent phase behavior and batch Cs distribution for waste simulants and real waste together with a preliminary flowsheet applicable for implementation in the MCU. The new solvent will enable MCU to process a much wider range of salt feeds and thereby extend its service lifetime beyond its design life of three years. Other potential benefits of NG-CSSX include increased throughput of the SRS Salt Waste Processing Facility (SWPF), currently under construction, and an alternative modular near-tank application at Hanford.« less

Critical assessment of three high performance liquid chromatography analytical methods for food carotenoid quantification.

PubMed

Dias, M Graça; Oliveira, Luísa; Camões, M Filomena G F C; Nunes, Baltazar; Versloot, Pieter; Hulshof, Paul J M

2010-05-21

Three sets of extraction/saponification/HPLC conditions for food carotenoid quantification were technically and economically compared. Samples were analysed for carotenoids alpha-carotene, beta-carotene, beta-cryptoxanthin, lutein, lycopene, and zeaxanthin. All methods demonstrated good performance in the analysis of a composite food standard reference material for the analytes they are applicable to. Methods using two serial connected C(18) columns and a mobile phase based on acetonitrile, achieved a better carotenoid separation than the method using a mobile phase based on methanol and one C(18)-column. Carotenoids from leafy green vegetable matrices appeared to be better extracted with a mixture of methanol and tetrahydrofuran than with tetrahydrofuran alone. Costs of carotenoid determination in foods were lower for the method with mobile phase based on methanol. However for some food matrices and in the case of E-Z isomer separations, this was not technically satisfactory. Food extraction with methanol and tetrahydrofuran with direct evaporation of these solvents, and saponification (when needed) using pyrogallol as antioxidant, combined with a HPLC system using a slight gradient mobile phase based on acetonitrile and a stationary phase composed by two serial connected C(18) columns was the most technically and economically favourable method. 2010. Published by Elsevier B.V.

PROCESS OF SEPARATING URANIUM FROM AQUEOUS SOLUTION BY SOLVENT EXTRACTION

DOEpatents

Warf, J.C.

1958-08-19

A process is described for separating uranium values from aqueous uranyl nitrate solutions. The process consists in contacting the uramium bearing solution with an organic solvent, tributyl phosphate, preferably diluted with a less viscous organic liquida whereby the uranyl nitrate is extracted into the organic solvent phase. The uranvl nitrate may be recovered from the solvent phase bv back extracting with an aqueous mediuin.

Development of biodegradable drug delivery system to treat addiction.

PubMed

Mandal, T K

1999-06-01

Opiate addiction is a serious problem that has now spread worldwide to all levels of society. Buprenorphine has been used for several years for the treatment of opiate addiction. The objective of this project was to develop sustained-release biodegradable microcapsules for the parenteral delivery of buprenorphine. Biodegradable microcapsules of buprenorphine/poly(lactide-co-glycolide) were prepared using two main procedures based on an in-water drying process in a complex emulsion system. These procedures differ in the way the organic solvent was eliminated: evaporation or extraction. The effect of drug loading and the effect of partial saturation of the aqueous phase with the core material during the in-water solvent evaporation were also studied. The efficiency of encapsulation increased from 11% to 34% when the drug loading was decreased from 20% to 5%. There was no significant change in the efficiency of encapsulation when the aqueous phase was partially saturated with buprenorphine. In changing the solvent removal process from evaporation to extraction, no significant change in the efficiency of encapsulation was observed. The microcapsules prepared by the solvent evaporation were smooth and spherical. However, the microcapsules prepared by the extraction of the organic solvent lost their surface smoothness and became slightly irregular and porous compared with the other batches. The average particle size of the microcapsules was between 14 and 49 microns. The cumulative drug release was between 2% and 4% within the first 24 hr. A sustained drug release continued over 45 days.

Comparative study of solvation parameter models accounting the effects of mobile phase composition in reversed-phase liquid chromatography.

PubMed

Torres-Lapasió, J R; Ruiz-Angel, M J; García-Alvarez-Coque, M C

2007-09-28

Solvation parameter models relate linearly compound properties with five fundamental solute descriptors (excess molar refraction, dipolarity/polarizability, effective hydrogen-bond acidity and basicity, and McGowan volume). These models are widely used, due to the availability of protocols to obtain the descriptors, good performance, and general applicability. Several approaches to predict retention in reversed-phase liquid chromatography (RPLC) as a function of these descriptors and mobile phase composition are compared, assaying the performance with a set of 146 organic compounds of diverse nature, eluted with acetonitrile and methanol. The approaches are classified in two groups: those that only allow predictions of retention for the mobile phases used to build the models, and those valid at any other mobile phase composition. The first group includes the use of ratios between the regressed coefficients of the solvation models that are assumed to be characteristic for a column/solvent system, and the application of offsets to transfer the retention from a reference mobile phase to any other. Maximal accuracy in predictions corresponded, however, to the approaches in the second group, which were based on models that describe the retention as a function of mobile phase composition (expressed as the solvent volume fraction or a normalised polarity measurement), where the coefficients were made dependent on the solvent descriptors. The study revealed the properties that influence the retention and distinguish the particular behaviour of acetonitrile and methanol in RPLC.

10.6% Certified Colloidal Quantum Dot Solar Cells via Solvent-Polarity-Engineered Halide Passivation.

PubMed

Lan, Xinzheng; Voznyy, Oleksandr; García de Arquer, F Pelayo; Liu, Mengxia; Xu, Jixian; Proppe, Andrew H; Walters, Grant; Fan, Fengjia; Tan, Hairen; Liu, Min; Yang, Zhenyu; Hoogland, Sjoerd; Sargent, Edward H

2016-07-13

Colloidal quantum dot (CQD) solar cells are solution-processed photovoltaics with broad spectral absorption tunability. Major advances in their efficiency have been made via improved CQD surface passivation and device architectures with enhanced charge carrier collection. Herein, we demonstrate a new strategy to improve further the passivation of CQDs starting from the solution phase. A cosolvent system is employed to tune the solvent polarity in order to achieve the solvation of methylammonium iodide (MAI) and the dispersion of hydrophobic PbS CQDs simultaneously in a homogeneous phase, otherwise not achieved in a single solvent. This process enables MAI to access the CQDs to confer improved passivation. This, in turn, allows for efficient charge extraction from a thicker photoactive layer device, leading to a certified solar cell power conversion efficiency of 10.6%, a new certified record in CQD photovoltaics.

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

PubMed

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

2014-01-01

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

Low-temperature glycerolysis of avocado oil

NASA Astrophysics Data System (ADS)

Satriana, Arpi, Normalina; Supardan, Muhammad Dani; Gustina, Rizka Try; Mustapha, Wan Aida Wan

2018-04-01

Glycerolysis can be a useful technique for production of mono- and diacylglycerols from triacylglycerols present in avocado oil. In the present work, the effect of catalyst and co-solvent concentration on low-temperature glycerolysis of avocado oil was investigated at 40oC of reaction temperature. A hydrodynamic cavitation system was used to enhance the miscibility of the oil and glycerol phases. NaOH and acetone were used as catalyst and co-solvent, respectively. The experimental results showed that the catalyst and co-solvent concentration affected the glycerolysis reaction rate. The catalyst concentration of 1.5% and co-solvent concentration of 300% were the optimised conditions. A suitable amount of NaOH and acetone must be added to achieve an optimum of triacylglycerol conversion.

Superhydrophobic perfluoropolymer/polystyrene blend films induced by nonsolvent

NASA Astrophysics Data System (ADS)

Gengec, Nevin Atalay; Cengiz, Ugur; Erbil, H. Yildirim

2016-10-01

Statistical copolymers of perfluoroalkyl ethyl acrylate (Zonyl-TAN) and methyl methacrylate (MMA) were synthesized in a CO2 polymerization system where a CO2-expanded monomer mixture was formed at 13 MPa, and 80 °C by using AIBN as initiator. Flat and superhydrophobic surfaces were subsequently prepared on glass slides by applying a phase separation process where the synthesized p(TAN-co-MMA) copolymer and polystyrene (PS) were dissolved in THF solvent. Ethanol was added as the non-solvent to introduce superhydrophobicity during film formation. Water contact angle on the flat p(TAN-co-MMA) copolymer was 118° and increased up to 170° with the formation of surface roughness. The ratio of the ethanol non-solvent in the blend solution has an important effect on the magnitude of surface roughness during the phase separation process. Both pits and protrusions of 1-10 μm in size were formed on the surface when non-solvent was used. Surface roughness increased with the increase in the ethanol ratio and the PS content of the blend solution.

High-speed counter-current chromatography in separation of betacyanins from flowers of red Gomphrena globosa L. cultivars.

PubMed

Spórna-Kucab, Aneta; Hołda, Ewelina; Wybraniec, Sławomir

2016-10-15

Antioxidant and possible chemopreventive properties of betacyanins, natural plant pigments, contribute to a growing interest in their chemistry and separation. Mixtures of betacyanins from fresh red Gomphrena globosa L. cultivar flowers were separated in three highly polar solvent systems by high-speed counter-current chromatography (HSCCC) for a direct comparison of their separation effectiveness. Three samples of crude extract (600mg) were run on semi-preparative scale in solvent system (NH4)2SO4soln - EtOH (2.0:1.0, v/v) (system I) and the modified systems: EtOH - ACN - 1-PrOH - (NH4)2SO4satd.soln - H2O (0.5:0.5:0.5:1.2:1.0, v/v/v/v/v) (system II) and EtOH - ACN - (NH4)2SO4satd.soln - H2O (1.0:0.5:1.2:1.0, v/v/v/v) (system III). The systems were used in the head-to-tail (system I) or tail-to-head (systems II and III) mode. The flow rate of the mobile phase was 2.0ml/min and the column rotation speed was 860rpm. The retention of the stationary phase was 52.0% (system I), 80.2% (systems II) and 82.0% (system III). The betacyanins in the crude extract as well as HSCCC fractions were analyzed by LC-MS/MS. System I was applied for the first time in HSCCC for the separation of betacyanins and was quite effective in separation of amaranthine and 17-decarboxy-amaranthine (αI=1.19) and very effective for 17-decarboxy-amaranthine and betanin (αI=2.20). Modification of system I with acetonitrile (system III) as well as acetonitrile and propanol (system II) increased their separation effectiveness. Systems II-III enable complete separation of 17-decarboxy-amaranthine (KD(II)=2.94,KD(III)=2.42) and betanin (KD(II)=2.46,KD(III)=1.10) as well as betanin and gomphrenin I (KD(II)=1.62, KD(III)=0.74). In addition, separation of amaranthine and 17-decarboxy-amaranthine is the most effective in system II, therefore, this system proved to be the most suitable for the separation of all polar betacyanins. Copyright © 2016 Elsevier B.V. All rights reserved.

EVALUATION OF ALTERNATIVES TO CHLORINATED SOLVENTS FOR METAL CLEANING

EPA Science Inventory

This project report details results of investigations into alternatives to chlorinated solvents used for metal degreasing. Three companies participated in this project. The results reported for one company document a situation where the conversion to an aqueous cleaning system ha...

Retention mechanism of hypercrosslinked polystyrene silica hybrid phase in normal phase chromatography.

PubMed

Wu, Di; Nedev, Georgi K; Lucy, Charles A

2014-11-28

Hypercrosslinked polystyrene phases have been described as quasi-normal phase because they lack discrete polar sites. Retention on the HC-Tol column is investigated using the Snyder-Soczewinski model. Solvent strength of different hexane-solvent binary mobile phase compositions can be predicted with solvent strength of pure dichloromethane (DCM, 0.159), tetrahydrofuran (THF, 0.22), and benzene (0.127). The HC-Tol column is shown to be a localizing adsorptive phase. Also, site-competition delocalization on HC-Tol demonstrates that whatever its adsorption groups are, they are able to participate in lateral interactions. Copyright © 2014 Elsevier B.V. All rights reserved.

Centrifugal contactor modified for end stage operation in a multistage system

DOEpatents

Jubin, Robert T.

1990-01-01

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

Optimization of the solvent-based dissolution method to sample volatile organic compound vapors for compound-specific isotope analysis.

PubMed

Bouchard, Daniel; Wanner, Philipp; Luo, Hong; McLoughlin, Patrick W; Henderson, James K; Pirkle, Robert J; Hunkeler, Daniel

2017-10-20

The methodology of the solvent-based dissolution method used to sample gas phase volatile organic compounds (VOC) for compound-specific isotope analysis (CSIA) was optimized to lower the method detection limits for TCE and benzene. The sampling methodology previously evaluated by [1] consists in pulling the air through a solvent to dissolve and accumulate the gaseous VOC. After the sampling process, the solvent can then be treated similarly as groundwater samples to perform routine CSIA by diluting an aliquot of the solvent into water to reach the required concentration of the targeted contaminant. Among solvents tested, tetraethylene glycol dimethyl ether (TGDE) showed the best aptitude for the method. TGDE has a great affinity with TCE and benzene, hence efficiently dissolving the compounds during their transition through the solvent. The method detection limit for TCE (5±1μg/m 3 ) and benzene (1.7±0.5μg/m 3 ) is lower when using TGDE compared to methanol, which was previously used (385μg/m 3 for TCE and 130μg/m 3 for benzene) [2]. The method detection limit refers to the minimal gas phase concentration in ambient air required to load sufficient VOC mass into TGDE to perform δ 13 C analysis. Due to a different analytical procedure, the method detection limit associated with δ 37 Cl analysis was found to be 156±6μg/m 3 for TCE. Furthermore, the experimental results validated the relationship between the gas phase TCE and the progressive accumulation of dissolved TCE in the solvent during the sampling process. Accordingly, based on the air-solvent partitioning coefficient, the sampling methodology (e.g. sampling rate, sampling duration, amount of solvent) and the final TCE concentration in the solvent, the concentration of TCE in the gas phase prevailing during the sampling event can be determined. Moreover, the possibility to analyse for TCE concentration in the solvent after sampling (or other targeted VOCs) allows the field deployment of the sampling method without the need to determine the initial gas phase TCE concentration. The simplified field deployment approach of the solvent-based dissolution method combined with the conventional analytical procedure used for groundwater samples substantially facilitates the application of CSIA to gas phase studies. Copyright © 2017 Elsevier B.V. All rights reserved.

Local phase separation of co-solvents enhances pretreatment of biomass for bioenergy applications

DOE PAGES

Mostofian, Barmak; Cai, Charles M.; Smith, Micholas Dean; ...

2016-08-02

Pretreatment facilitates more complete deconstruction of plant biomass to enable more economic production of lignocellulosic biofuels and byproducts. Various co-solvent pretreatments have demonstrated advantages relative to aqueous-only methods by enhancing lignin removal to allow unfettered access to cellulose. However, there is a limited mechanistic understanding of the interactions between the co-solvents and cellulose that impedes further improvement of such pretreatment methods. Recently, tetrahydrofuran (THF) has been identified as a highly effective co-solvent for the pretreatment and fractionation of biomass. Here, to elucidate the mechanism of the THF water interactions with cellulose, we pair simulation and experimental data demonstrating that enhancedmore » solubilization of cellulose can be achieved by the THF water co-solvent system at equivolume mixtures and moderate temperatures (≤445 K). The simulations show that THF and water spontaneously phase separate on the local surface of a cellulose fiber, owing to hydrogen bonding of water molecules with the hydrophilic cellulose faces and stacking of THF molecules on the hydrophobic faces. Furthermore, a single fully solvated cellulose chain is shown to be preferentially bound by water molecules in the THF water mixture. In light of these findings, co-solvent reactions were performed on microcrystalline cellulose and maple wood to show that THF significantly enhanced cellulose deconstruction and lignocellulose solubilization at simulation conditions, enabling a highly versatile and efficient biomass pretreatment and fractionation method.« less

Cleanliness verification process at Martin Marietta Astronautics

NASA Astrophysics Data System (ADS)

King, Elizabeth A.; Giordano, Thomas J.

1994-06-01

The Montreal Protocol and the 1990 Clean Air Act Amendments mandate CFC-113, other chlorinated fluorocarbons (CFC's) and 1,1,1-Trichloroethane (TCA) be banned from production after December 31, 1995. In response to increasing pressures, the Air Force has formulated policy that prohibits purchase of these solvents for Air Force use after April 1, 1994. In response to the Air Force policy, Martin Marietta Astronautics is in the process of eliminating all CFC's and TCA from use at the Engineering Propulsion Laboratory (EPL), located on Air Force property PJKS. Gross and precision cleaning operations are currently performed on spacecraft components at EPL. The final step of the operation is a rinse with a solvent, typically CFC-113. This solvent is then analyzed for nonvolatile residue (NVR), particle count and total filterable solids (TFS) to determine cleanliness of the parts. The CFC-113 used in this process must be replaced in response to the above policies. Martin Marietta Astronautics, under contract to the Air Force, is currently evaluating and testing alternatives for a cleanliness verification solvent. Completion of test is scheduled for May, 1994. Evaluation of the alternative solvents follows a three step approach. This first is initial testing of solvents picked from literature searches and analysis. The second step is detailed testing of the top candidates from the initial test phase. The final step is implementation and validation of the chosen alternative(s). Testing will include contaminant removal, nonvolatile residue, material compatibility and propellant compatibility. Typical materials and contaminants will be tested with a wide range of solvents. Final results of the three steps will be presented as well as the implementation plan for solvent replacement.

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.

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

Wilden, Andreas; Lumetta, Gregg J.; Sadowski, Fabian

A solvent extraction system has been developed for separating trivalent actinides from lanthanides. This “Advanced TALSPEAK” system uses 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester to extract the lanthanides into a n-dodecane-based solvent phase, while the actinides are retained in a citrate-buffered aqueous phase by complexation to N-(2-hydroxyethyl)ethylenediamine-N,N',N'-triacetic acid. Batch distribution measurements indicate that the separation of americium from the light lanthanides decreases as the pH decreases. For example, the separation factor between La and Am increases from 2.5 at pH 2.0 to 19.3 at pH 3.0. However, previous investigations indicated that the extraction rates for the heavier lanthanides decrease with increasing pH.more » So, a balance between these two competing effects is required. An aqueous phase in which the pH was set at 2.6 was chosen for further process development because this offered optimal separation, with a minimum separation factor of ~8.4, based on the separation between La and Am. Centrifugal contactor single-stage efficiencies were measured to characterize the performance of the system under flow conditions.« less

A novel method to augment extraction of mangiferin by application of microwave on three phase partitioning.

PubMed

Kulkarni, Vrushali M; Rathod, Virendra K

2015-06-01

This work reports a novel approach where three phase partitioning (TPP) was combined with microwave for extraction of mangiferin from leaves of Mangifera indica . Soxhlet extraction was used as reference method, which yielded 57 mg/g in 5 h. Under optimal conditions such as microwave irradiation time 5 min, ammonium sulphate concentration 40% w/v, power 272 W, solute to solvent ratio 1:20, slurry to t -butanol ratio 1:1, soaking time 5 min and duty cycle 50%, the mangiferin yield obtained was 54 mg/g by microwave assisted three phase partitioning extraction (MTPP). Thus extraction method developed resulted into higher extraction yield in a shorter span, thereby making it an interesting alternative prior to down-stream processing.

The mechanism for water exchange in [UO(2)(H(2)O)(5)](2+) and [UO(2)(oxalate)(2)(H(2)O)](2-), as studied by quantum chemical methods.

PubMed

Vallet, V; Wahlgren, U; Schimmelpfennig, B; Szabó, Z; Grenthe, I

2001-12-05

The mechanisms for the exchange of water between [UO(2)(H(2)O)(5)](2+), [UO(2)(oxalate)(2)(H(2)O)](2)(-)(,) and water solvent along dissociative (D), associative (A) and interchange (I) pathways have been investigated with quantum chemical methods. The choice of exchange mechanism is based on the computed activation energy and the geometry of the identified transition states and intermediates. These quantities were calculated both in the gas phase and with a polarizable continuum model for the solvent. There is a significant and predictable difference between the activation energy of the gas phase and solvent models: the energy barrier for the D-mechanism increases in the solvent as compared to the gas phase, while it decreases for the A- and I-mechanisms. The calculated activation energy, Delta U(++), for the water exchange in [UO(2)(H(2)O)(5)](2+) is 74, 19, and 21 kJ/mol, respectively, for the D-, A-, and I-mechanisms in the solvent, as compared to the experimental value Delta H(++) = 26 +/- 1 kJ/mol. This indicates that the D-mechanism for this system can be ruled out. The energy barrier between the intermediates and the transition states is small, indicating a lifetime for the intermediate approximately 10(-10) s, making it very difficult to distinguish between the A- and I-mechanisms experimentally. There is no direct experimental information on the rate and mechanism of water exchange in [UO(2)(oxalate)(2)(H(2)O)](2-) containing two bidentate oxalate ions. The activation energy and the geometry of transition states and intermediates along the D-, A-, and I-pathways were calculated both in the gas phase and in a water solvent model, using a single-point MP2 calculation with the gas phase geometry. The activation energy, Delta U(++), in the solvent for the D-, A-, and I-mechanisms is 56, 12, and 53 kJ/mol, respectively. This indicates that the water exchange follows an associative reaction mechanism. The geometry of the A- and I-transition states for both [UO(2)(H(2)O)(5)](2+) and [UO(2)(oxalate)(2)(H(2)O)](2-) indicates that the entering/leaving water molecules are located outside the plane formed by the spectator ligands.

Separation of polar betalain pigments from cacti fruits of Hylocereus polyrhizus by ion-pair high-speed countercurrent chromatography.

PubMed

Wybraniec, Sławomir; Stalica, Paweł; Jerz, Gerold; Klose, Bettina; Gebers, Nadine; Winterhalter, Peter; Spórna, Aneta; Szaleniec, Maciej; Mizrahi, Yosef

2009-10-09

Polar betacyanin pigments together with betaxanthins from ripe cactus fruits of Hylocereus polyrhizus (Cactaceae) were fractionated by means of preparative ion-pair high-speed countercurrent chromatography (IP-HSCCC) also using the elution-extrusion (EE) approach for a complete pigment recovery. HSCCC separations were operated in the classical 'head-to-tail' mode with an aqueous mobile phase. Different CCC solvent systems were evaluated in respect of influence and effectiveness of fractionation capabilities to separate the occurring pigment profile of H. polyrhizus. For that reason, the additions of two different volatile ion-pair forming perfluorinated carboxylic acids (PFCA) were investigated. For a direct comparison, five samples of Hylocereus pigment extract were run on preparative scale (900 mg) in 1-butanol-acetonitrile-aqueous TFA 0.7% (5:1:6, v/v/v) and the modified systems tert.-butyl methyl ether-1-butanol-acetonitrile-aqueous PFCA (2:2:1:5, v/v/v/v) using 0.7% and 1.0% trifluoroacetic acid (TFA) or heptafluorobutyric acid (HFBA) in the aqueous phase, respectively. The chemical affinity to the organic stationary CCC solvent phases and in consequence the retention of these highly polar betalain pigments was significantly increased by the use of the more lipophilic fluorinated ion-pair reagent HFBA instead of TFA. The HFBA additions separated more effectively the typical cacti pigments phyllocactin and hylocerenin from betanin as well as their iso-forms. Unfortunately, similar K(D) ratios and selectivity factors alpha around 1.0-1.1 in all tested solvent systems proved that the corresponding diastereomers, 15S-type pigments cannot be resolved from the 15R-epimers (iso-forms). Surprisingly, additions of the stronger ion-pair reagent (HFBA) resulted in a partial separation of hylocerenin from phyllocactin which were not resolved in the other solvent systems. The pigments were detected by means of HPLC-DAD and HPLC-electrospray ionization-MS using also authentic reference materials.

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.

Preparative enantiomer separation of dichlorprop with a cinchona-derived chiral selector employing centrifugal partition chromatography and high-performance liquid chromatography: a comparative study.

PubMed

Gavioli, Elena; Maier, Norbert M; Minguillón, Cristina; Lindner, Wolfgang

2004-10-01

A countercurrent chromatography protocol for support-free preparative enantiomer separation of the herbicidal agent 2-(2,4-dichlorphenoxy)propionic acid (dichlorprop) was developed utilizing a purposefully designed, highly enantioselective chiral stationary-phase additive (CSPA) derived from bis-1,4-(dihydroquinidinyl)phthalazine. Guided by liquid-liquid extraction experiments, a solvent system consisting of 10 mM CSPA in methyl tert-butyl ether and 100 mM sodium phosphate buffer (pH 8.0) was identified as a suitable stationary/mobile-phase combination. This solvent system provided an ideal compromise among stationary-phase retention, enantioselectivity, and well-balanced analyte distribution behavior. Using a commercial centrifugal partition chromatography instrument, complete enantiomer separations of up to 366 mg of racemic dichlorprop could be achieved, corresponding to a sample load being equivalent to the molar amount of CSPA employed. Comparison of the preparative performance characteristics of the CPC protocol with that of a HPLC separation using a silica-supported bis-1,4-(dihydroquinidinyl)phthalazine chiral stationary phase CSP revealed comparable loading capacities for both techniques but a significantly lower solvent consumption for CPC. With respect to productivity, HPLC was found to be superior, mainly due to inherent flow rate restrictions of the CPC instrument. Given that further progress in instrumental design and engineering of dedicated, highly enantioselective CSPAs can be achieved, CPC may offer a viable alternative to CSP-based HPLC for preparative-scale enantiomer separation.

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

Separation by solvent extraction

DOEpatents

Holt, Jr., Charles H.

1976-04-06

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

Assembly of 4-, 6- and 8-connected Cd(II) pseudo-polymorphic coordination polymers: Synthesis, solvent-dependent structural variation and properties

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

Li, Zhao-Hao; Xue, Li-Ping, E-mail: lpxue@163.com; Miao, Shao-Bin

2016-08-15

The reaction of Cd(NO{sub 3}){sub 2}·4H{sub 2}O, 2,5-thiophenedicarboxylic acid (H{sub 2}tdc) and 1,2-bis(imidazol-1′-yl)methane (bimm) by modulating solvent systems yielded three highly connected pseudo-polymorphic coordination polymers based on different dinuclear [Cd{sub 2}(CO{sub 2}){sub 2}] subunits bridged by carboxylate groups. Single crystal structural analyses reveal structural variation from 4-connected 2D sql layer, 6-connected 2-fold interpenetrated 3D pcu to 8-connected 3D bcu-type network in compounds 1–3. The structural dissimilarity in the structures dependent on the coordination environments of Cd(II) ions and linking modes of mixed ligand influenced by different solvent systems during the synthesis process. Moreover, thermogravimetric and photoluminescence behaviors of 1–3 weremore » also investigated for the first time, and all the complexes emit blue luminescence in the solid state. - Graphical abstract: Key Topic. Different solvent systems modulated three Cd(II) pseudo-polymorphic coordination polymers based on thiophene-2,5-dicarboxylate and 1,2-bis(imidazol-1′-yl)methane mixed ligands. Display Omitted - Highlights: • Three solvent-dependent Cd(II) pseudo-polymorphic coordination polymers have been synthesized. • Structural variation from 4-connected 2D layer, 6-connected 2-fold interpenetrated 3D net to 8-connected 3D net. • All complexes emit blue luminescence.« less

Method of separating lignocellulosic material into lignin, cellulose and dissolved sugars

DOEpatents

Black, S.K.; Hames, B.R.; Myers, M.D.

1998-03-24

A method is described for separating lignocellulosic material into (a) lignin, (b) cellulose, and (c) hemicellulose and dissolved sugars. Wood or herbaceous biomass is digested at elevated temperature in a single-phase mixture of alcohol, water and a water-immiscible organic solvent (e.g., a ketone). After digestion, the amount of water or organic solvent is adjusted so that there is phase separation. The lignin is present in the organic solvent, the cellulose is present in a solid pulp phase, and the aqueous phase includes hemicellulose and any dissolved sugars.

Method of separating lignocellulosic material into lignin, cellulose and dissolved sugars

DOEpatents

Black, Stuart K.; Hames, Bonnie R.; Myers, Michele D.

1998-01-01

A method for separating lignocellulosic material into (a) lignin, (b) cellulose, and (c) hemicellulose and dissolved sugars. Wood or herbaceous biomass is digested at elevated temperature in a single-phase mixture of alcohol, water and a water-immiscible organic solvent (e.g., a ketone). After digestion, the amount of water or organic solvent is adjusted so that there is phase separation. The lignin is present in the organic solvent, the cellulose is present in a solid pulp phase, and the aqueous phase includes hemicellulose and any dissolved sugars.

Method of drying articles

DOEpatents

Janney, Mark A.; Kiggans, Jr., James O.

1999-01-01

A method of drying a green particulate article includes the steps of: a. Providing a green article which includes a particulate material and a pore phase material, the pore phase material including a solvent; and b. contacting the green article with a liquid desiccant for a period of time sufficient to remove at least a portion of the solvent from the green article, the pore phase material acting as a semipermeable barrier to allow the solvent to be sorbed into the liquid desiccant, the pore phase material substantially preventing the liquid desiccant from entering the pores.

Membrane assisted solvent extraction for rare earth element recovery

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

Bhave, Ramesh R.; Kim, Daejin; Peterson, Eric S.

Systems and methods for the recovery of rare earth elements are provided. The systems and methods generally include membrane assisted solvent extraction using permeable hollow fibers having an immobilized organic phase within the pores of the hollow fibers. The permeable hollow fibers are generally in contact with an acidic aqueous feed on one side thereof and a strip solution on another side thereof. The systems and methods generally include the simultaneous extraction and stripping of rare earth elements as a continuous recovery process that is well suited for post-consumer products, end-of-life products, and other recovery sources of rare earth elements.

Effects of Organic Solvents on Indigo Formation by Pseudomonas sp. strain ST-200 Grown with High Levels of Indole.

PubMed

Doukyu, N; Arai, T; Aono, R

1998-01-01

The indole tolerance level of Pseudomonas sp. strain ST-200 was 0.25 mg/ml. The level was raised to 4 mg/ml when diphenylmethane was added to the medium to 20% by volume. ST-200 grown in this two-phase culture system containing indole (1 mg/ml) and diphenylmethane (0.2 ml/ml) produced a water-soluble yellow pigment, isatic acid, and two water-insoluble and diphenylmethane-soluble pigments, blue indigo and purple indirubin. The amounts of the water-insoluble pigments corresponded to 0.5% (indigo) and 0.2% (indirubin) of the indole added to the medium. Of the conditions tried, indigo and indirubin were formed only when ST-200 was grown in the two-phase system overlaid with organic solvents with appropriate polarity.

Conformational and bioactivity analysis of insulin: freeze-drying TBA/water co-solvent system in the presence of surfactant and sugar.

PubMed

Zhang, Yong; Deng, Yingjie; Wang, Xueli; Xu, Jinghua; Li, Zhengqiang

2009-04-17

Despite the extensive research into the freeze-drying of aqueous solutions of proteins, it remains unknown whether proteins can survive the lyophilization process in a water-organic co-solvent system and how the process and additives affect the structural stability and activity of the proteins. In the present study, a conformational analysis of insulin in the absence/presence of bile salt and trehalose was carried out, before and after freeze-drying of a tert-butyl alcohol (TBA)/water co-solvent system at volume ratios of TBA to water ranging from 50/50 to 0/100. The study involved the use of ultraviolet derivative and fluorescence spectroscopy, circular dichroism (CD) and Fourier transform infrared (FTIR) spectroscopy. Also the bioactivity of insulin was evaluated in vivo using the streptozotocin (STZ)-induced diabetic mice as an animal model. Initial investigations indicate that the extent of the structural change of insulin depends significantly both on the TBA content and on the concentration of additives, such as sodium deoxycholate, prior to lyophilization. This could be accounted for by the phase behavior properties of the TBA/water co-solvent system, surface denaturation together with the selective and/or forced dispersion of insulin during phase separation. Lyophilized insulin in the presence of bile salt and trehalose retained more of its bioactivity and native-like structure in the solid state compared with that in the absence of additives at various TBA/water ratios, although in all cases there was a major and reversible rearrangement of secondary structure after rehydration, except for insulin at 50% TBA (v/v). Furthermore, both lyophilization in non-eutectic systems and less structural changes in the formulation process lead to more bioactivity.

Complexation and phase evolution at dimethylformamide-Ag(111) interfaces

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

Song, Wentao; Leung, Kevin; Shao, Qian

The interaction of solvent molecules with metallic surfaces impacts many interfacial chemical processes. We investigate the chemical and structure evolution that follows adsorption of the polar solvent dimethylformamide (DMF) on Ag(111). An Ag(DMF) 2 coordination complex forms spontaneously by DMF etching of Ag(111), yielding mixed films of the complexes and DMF. Utilizing ultrahigh vacuum scanning tunneling microscopy (UHV-STM), in combination with X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT) computations, we map monolayer phases from the 2-D gas regime, consisting of a binary mixture of DMF and Ag(DMF) 2, through the saturation monolayer limit, in which these two chemicalmore » species phase separate into ordered islands. Structural models for the near-square DMF phase and the chain-like Ag(DMF) 2 phase are presented and supported by DFT computation. Interface evolution is summarized in a surface pressure-composition phase diagram, which allows structure prediction over arbitrary experimental conditions. In conclusion, this work reveals new surface coordination chemistry for an important electrolyte-electrode system, and illustrates how surface pressure can be used to tune monolayer phases.« less

Complexation and phase evolution at dimethylformamide-Ag(111) interfaces

DOE PAGES

Song, Wentao; Leung, Kevin; Shao, Qian; ...

2016-09-15

The interaction of solvent molecules with metallic surfaces impacts many interfacial chemical processes. We investigate the chemical and structure evolution that follows adsorption of the polar solvent dimethylformamide (DMF) on Ag(111). An Ag(DMF) 2 coordination complex forms spontaneously by DMF etching of Ag(111), yielding mixed films of the complexes and DMF. Utilizing ultrahigh vacuum scanning tunneling microscopy (UHV-STM), in combination with X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT) computations, we map monolayer phases from the 2-D gas regime, consisting of a binary mixture of DMF and Ag(DMF) 2, through the saturation monolayer limit, in which these two chemicalmore » species phase separate into ordered islands. Structural models for the near-square DMF phase and the chain-like Ag(DMF) 2 phase are presented and supported by DFT computation. Interface evolution is summarized in a surface pressure-composition phase diagram, which allows structure prediction over arbitrary experimental conditions. In conclusion, this work reveals new surface coordination chemistry for an important electrolyte-electrode system, and illustrates how surface pressure can be used to tune monolayer phases.« less

Advanced Amine Solvent Formulations and Process Integration for Near-Term CO2 Capture Success

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

Fisher, Kevin S.; Searcy, Katherine; Rochelle, Gary T.

2007-06-28

This Phase I SBIR project investigated the economic and technical feasibility of advanced amine scrubbing systems for post-combustion CO2 capture at coal-fired power plants. Numerous combinations of advanced solvent formulations and process configurations were screened for energy requirements, and three cases were selected for detailed analysis: a monoethanolamine (MEA) base case and two “advanced” cases: an MEA/Piperazine (PZ) case, and a methyldiethanolamine (MDEA) / PZ case. The MEA/PZ and MDEA/PZ cases employed an advanced “double matrix” stripper configuration. The basis for calculations was a model plant with a gross capacity of 500 MWe. Results indicated that CO2 capture increased themore » base cost of electricity from 5 cents/kWh to 10.7 c/kWh for the MEA base case, 10.1 c/kWh for the MEA / PZ double matrix, and 9.7 c/kWh for the MDEA / PZ double matrix. The corresponding cost per metric tonne CO2 avoided was 67.20 $/tonne CO2, 60.19 $/tonne CO2, and 55.05 $/tonne CO2, respectively. Derated capacities, including base plant auxiliary load of 29 MWe, were 339 MWe for the base case, 356 MWe for the MEA/PZ double matrix, and 378 MWe for the MDEA / PZ double matrix. When compared to the base case, systems employing advanced solvent formulations and process configurations were estimated to reduce reboiler steam requirements by 20 to 44%, to reduce derating due to CO2 capture by 13 to 30%, and to reduce the cost of CO2 avoided by 10 to 18%. These results demonstrate the potential for significant improvements in the overall economics of CO2 capture via advanced solvent formulations and process configurations.« less

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.

A Non-catalytic Deep Desulphurization Process using Hydrodynamic Cavitation

PubMed Central

Suryawanshi, Nalinee B.; Bhandari, Vinay M.; Sorokhaibam, Laxmi Gayatri; Ranade, Vivek V.

2016-01-01

A novel approach is developed for desulphurization of fuels or organics without use of catalyst. In this process, organic and aqueous phases are mixed in a predefined manner under ambient conditions and passed through a cavitating device. Vapor cavities formed in the cavitating device are then collapsed which generate (in-situ) oxidizing species which react with the sulphur moiety resulting in the removal of sulphur from the organic phase. In this work, vortex diode was used as a cavitating device. Three organic solvents (n-octane, toluene and n-octanol) containing known amount of a model sulphur compound (thiophene) up to initial concentrations of 500 ppm were used to verify the proposed method. A very high removal of sulphur content to the extent of 100% was demonstrated. The nature of organic phase and the ratio of aqueous to organic phase were found to be the most important process parameters. The results were also verified and substantiated using commercial diesel as a solvent. The developed process has great potential for deep of various organics, in general, and for transportation fuels, in particular. PMID:27605492

A Non-catalytic Deep Desulphurization Process using Hydrodynamic Cavitation.

PubMed

Suryawanshi, Nalinee B; Bhandari, Vinay M; Sorokhaibam, Laxmi Gayatri; Ranade, Vivek V

2016-09-08

A novel approach is developed for desulphurization of fuels or organics without use of catalyst. In this process, organic and aqueous phases are mixed in a predefined manner under ambient conditions and passed through a cavitating device. Vapor cavities formed in the cavitating device are then collapsed which generate (in-situ) oxidizing species which react with the sulphur moiety resulting in the removal of sulphur from the organic phase. In this work, vortex diode was used as a cavitating device. Three organic solvents (n-octane, toluene and n-octanol) containing known amount of a model sulphur compound (thiophene) up to initial concentrations of 500 ppm were used to verify the proposed method. A very high removal of sulphur content to the extent of 100% was demonstrated. The nature of organic phase and the ratio of aqueous to organic phase were found to be the most important process parameters. The results were also verified and substantiated using commercial diesel as a solvent. The developed process has great potential for deep of various organics, in general, and for transportation fuels, in particular.

A Non-catalytic Deep Desulphurization Process using Hydrodynamic Cavitation

NASA Astrophysics Data System (ADS)

Suryawanshi, Nalinee B.; Bhandari, Vinay M.; Sorokhaibam, Laxmi Gayatri; Ranade, Vivek V.

2016-09-01

A novel approach is developed for desulphurization of fuels or organics without use of catalyst. In this process, organic and aqueous phases are mixed in a predefined manner under ambient conditions and passed through a cavitating device. Vapor cavities formed in the cavitating device are then collapsed which generate (in-situ) oxidizing species which react with the sulphur moiety resulting in the removal of sulphur from the organic phase. In this work, vortex diode was used as a cavitating device. Three organic solvents (n-octane, toluene and n-octanol) containing known amount of a model sulphur compound (thiophene) up to initial concentrations of 500 ppm were used to verify the proposed method. A very high removal of sulphur content to the extent of 100% was demonstrated. The nature of organic phase and the ratio of aqueous to organic phase were found to be the most important process parameters. The results were also verified and substantiated using commercial diesel as a solvent. The developed process has great potential for deep of various organics, in general, and for transportation fuels, in particular.

Inorganic metal oxide/organic polymer nanocomposites and method thereof

DOEpatents

Gash, Alexander E.; Satcher, Joe H.; Simpson, Randy

2004-03-30

A synthetic method for preparation of hybrid inorganic/organic energetic nanocomposites is disclosed herein. The method employs the use of stable metal inorganic salts and organic solvents as well as an organic polymer with good solubility in the solvent system to produce novel nanocomposite energetic materials. In addition, fuel metal powders (particularly those that are oxophillic) can be incorporated into composition. This material has been characterized by thermal methods, energy-filtered transmission electron microscopy (EFTEM), N.sub.2 adsoprtion/desorption methods, and Fourier-Transform (FT-IR) spectroscopy. According to these characterization methods the organic polymer phase fills the nanopores of the composite material, providing superb mixing of the component phases in the energetic nanocomposite.

Inorganic Metal Oxide/Organic Polymer Nanocomposites And Method Thereof

DOEpatents

Gash, Alexander E.; Satcher, Joe H.; Simpson, Randy

2004-11-16

A synthetic method for preparation of hybrid inorganic/organic energetic nanocomposites is disclosed herein. The method employs the use of stable metal in organic salts and organic solvents as well as an organic polymer with good solubility in the solvent system to produce novel nanocomposite energetic materials. In addition, fuel metal powders (particularly those that are oxophilic) can be incorporated into composition. This material has been characterized by thermal methods, energy-filtered transmission electron microscopy (EFTEM), N.sub.2 adsoprtion/desorption methods, and Fourier-Transform (FT-IR) spectroscopy. According to these characterization methods the organic polymer phase fills the nanopores of the material, providing superb mixing of the component phases in the energetic nanocomposite.

Optimization of minoxidil microemulsions using fractional factorial design approach.

PubMed

Jaipakdee, Napaphak; Limpongsa, Ekapol; Pongjanyakul, Thaned

2016-01-01

The objective of this study was to apply fractional factorial and multi-response optimization designs using desirability function approach for developing topical microemulsions. Minoxidil (MX) was used as a model drug. Limonene was used as an oil phase. Based on solubility, Tween 20 and caprylocaproyl polyoxyl-8 glycerides were selected as surfactants, propylene glycol and ethanol were selected as co-solvent in aqueous phase. Experiments were performed according to a two-level fractional factorial design to evaluate the effects of independent variables: Tween 20 concentration in surfactant system (X1), surfactant concentration (X2), ethanol concentration in co-solvent system (X3), limonene concentration (X4) on MX solubility (Y1), permeation flux (Y2), lag time (Y3), deposition (Y4) of MX microemulsions. It was found that Y1 increased with increasing X3 and decreasing X2, X4; whereas Y2 increased with decreasing X1, X2 and increasing X3. While Y3 was not affected by these variables, Y4 increased with decreasing X1, X2. Three regression equations were obtained and calculated for predicted values of responses Y1, Y2 and Y4. The predicted values matched experimental values reasonably well with high determination coefficient. By using optimal desirability function, optimized microemulsion demonstrating the highest MX solubility, permeation flux and skin deposition was confirmed as low level of X1, X2 and X4 but high level of X3.

Development of a Matrix Solid-Phase Dispersion Extraction Combined with UPLC/Q-TOF-MS for Determination of Phenolics and Terpenoids from the Euphorbia fischeriana.

PubMed

Li, Wenjing; Lin, Yu; Wang, Yuchun; Hong, Bo

2017-09-11

A method based on a simplified extraction by matrix solid phase dispersion (MSPD) followed by ultra-performance liquid chromatography coupled with the quadrupole time-of-flight tandem mass spectrometry (UPLC/Q-TOF-MS) determination is validated for analysis of two phenolics and three terpenoids in Euphorbia fischeriana . The optimized experimental parameters of MSPD including dispersing sorbent (silica gel), ratio of sample to dispersing sorbent (1:2), elution solvent (water-ethanol: 30-70) and volume of the elution solvent (10 mL) were examined and set down. The highest extraction yields of chromatogram information and the five compounds were obtained under the optimized conditions. A total of 25 constituents have been identified and five components have been quantified from Euphorbia fischeriana . A linear relationship (r² ≥ 0.9964) between the concentrations and the peak areas of the mixed standard substances were revealed. The average recovery was between 92.4% and 103.2% with RSD values less than 3.45% ( n = 5). The extraction yields of two phenolics and three terpenoids obtained by the MSPD were higher than those of traditional reflux and sonication extraction with reduced requirement on sample, solvent and time. In addition, the optimized method will be applied for analyzing terpenoids in other Chinese herbal medicine samples.

Ternary Phase-Separation Investigation of Sol-Gel Derived Silica from Ethyl Silicate 40

PubMed Central

Wang, Shengnan; Wang, David K.; Smart, Simon; Diniz da Costa, João C.

2015-01-01

A ternary phase-separation investigation of the ethyl silicate 40 (ES40) sol-gel process was conducted using ethanol and water as the solvent and hydrolysing agent, respectively. This oligomeric silica precursor underwent various degrees of phase separation behaviour in solution during the sol-gel reactions as a function of temperature and H2O/Si ratios. The solution composition within the immiscible region of the ES40 phase-separated system shows that the hydrolysis and condensation reactions decreased with decreasing reaction temperature. A mesoporous structure was obtained at low temperature due to weak drying forces from slow solvent evaporation on one hand and formation of unreacted ES40 cages in the other, which reduced network shrinkage and produced larger pores. This was attributed to the concentration of the reactive sites around the phase-separated interface, which enhanced the condensation and crosslinking. Contrary to dense silica structures obtained from sol-gel reactions in the miscible region, higher microporosity was produced via a phase-separated sol-gel system by using high H2O/Si ratios. This tailoring process facilitated further condensation reactions and crosslinking of silica chains, which coupled with stiffening of the network, made it more resistant to compression and densification. PMID:26411484

Analysis of solvent induced porous PMMA-Bioglass monoliths by the phase separation method--mechanical and in vitro biocompatible studies.

PubMed

Durgalakshmi, D; Balakumar, S

2015-01-14

Mimicking three dimensional microstructural scaffolds with their requisite mechanical properties in relation to human bone is highly needed for implant applications. Various biocompatible polymers and bioactive glasses were synthesized to achieve these properties. In the present study, we have fabricated highly porous and bioactive PMMA-Bioglass scaffolds by the phase separation method. Chloroform, acetone and an ethanol-water mixture were used as the different solvent phases in preparing the scaffolds. Large interconnecting pores of sizes ∼100 to 250 μm were observed in the scaffolds and a porosity percentage up to 54% was also achieved by this method. All samples showed a brittle fracture with the highest modulus of 91 MPa for the ethanol-water prepared scaffolds. The bioactivities of the scaffolds were further studied by immersing them in simulated body fluid for 28 days. Scanning electron microscopy, X-ray diffraction and Raman spectra confirmed the formation of bioactive hydroxyl calcium apatite on the surfaces of the scaffolds.

Analysis of Compounds Dissolved in Nonpolar Solvents by Electrospray Ionization on Conductive Nanomaterials

NASA Astrophysics Data System (ADS)

Xia, Bing; Gao, Yuanji; Ji, Baocheng; Ma, Fengwei; Ding, Lisheng; Zhou, Yan

2018-03-01

Electrospray ionization mass spectrometry (ESI-MS) technique has limitations in analysis of compounds that are dissolved in nonpolar solvents. In this study, ambient ionization of compounds in solvents that are not "friendly" to electrospray ionization, such as n-hexane, is achieved by conductive nanomaterials spray ionization (CNMSI) on nanomaterial emitters, including carbon nanotubes paper and mesodendritic silver covered metal, which applies high voltages to emitters made of these materials without the assistance of polar solvents. Although the time intensity curves (TIC) commonly vary from 4.5% to 23.7% over analyses, protonated molecular ions were found to be the most abundant species, demonstrating good reproducibility of the technique in terms of ionized species. Higher mass spectrometric responses are observed in analyzing nonpolar systems than polar systems. 2-Methoxyacetophenone, 4-methylacetophenone, benzothiazole, quinolone, and cycloheptanone as low as 2 pg in n-hexane can be directly detected using the developed method. The developed technique expands the analysis capability of ESI-MS for direct, online analysis of nonpolar systems, such as low polarity extracts, normal phase liquid chromatography eluates, and synthetic mixtures. [Figure not available: see fulltext.

Quantum Monte Carlo studies of solvated systems

NASA Astrophysics Data System (ADS)

Schwarz, Kathleen; Letchworth Weaver, Kendra; Arias, T. A.; Hennig, Richard G.

2011-03-01

Solvation qualitatively alters the energetics of diverse processes from protein folding to reactions on catalytic surfaces. An explicit description of the solvent in quantum-mechanical calculations requires both a large number of electrons and exploration of a large number of configurations in the phase space of the solvent. These problems can be circumvented by including the effects of solvent through a rigorous classical density-functional description of the liquid environment, thereby yielding free energies and thermodynamic averages directly, while eliminating the need for explicit consideration of the solvent electrons. We have implemented and tested this approach within the CASINO Quantum Monte Carlo code. Our method is suitable for calculations in any basis within CASINO, including b-spline and plane wave trial wavefunctions, and is equally applicable to molecules, surfaces, and crystals. For our preliminary test calculations, we use a simplified description of the solvent in terms of an isodensity continuum dielectric solvation approach, though the method is fully compatible with more reliable descriptions of the solvent we shall employ in the future.

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

Betterton, E.A.; Arnold, R.G.; Liu, Zhijie

Three abiotic systems are described that catalyze the reductive dehalogenation of heavily halogenated environmental pollutants, including carbon tetrachloride, trichloroethene, and perchloroethene. These systems include (a) an electrolytic reactor in which the potential on the working electrode (cathode) is fixed by using a potentiostat, (b) a light-driven system consisting of a semiconductor and (covalently attached) macrocycle that can accept light transmitted via an optical fiber, and a light-driven, two-solvent (isopropanol/acetone) system that promotes dehalogenation reactions via an unknown mechanism. Each is capable of accelerating reductive dehalogenation reactions to very high rates under laboratory conditions. Typically, millimolar concentrations of aqueous-phase targets canmore » be dehalogenated in minutes to hours. The description of each system includes the elements of reaction mechanism (to the extent known), typical kinetic data, and a discussion of the feasibility of applying this technology for the in situ destruction of hazardous compounds. 14 refs., 11 figs., 2 tabs.« less

Transformation of eutectic emulsion to nanosuspension fabricating with solvent evaporation and ultrasonication technique

PubMed Central

Phaechamud, Thawatchai; Tuntarawongsa, Sarun

2016-01-01

Eutectic solvent can solubilize high amount of some therapeutic compounds. Volatile eutectic solvent is interesting to be used as solvent in the preparation of nanosuspension with emulsion solvent evaporation technique. The mechanism of transformation from the eutectic emulsion to nanosuspension was investigated in this study. The 30% w/w ibuprofen eutectic solution was used as the internal phase, and the external phase is composed of Tween 80 as emulsifier. Ibuprofen nanosuspension was prepared by eutectic emulsion solvent evaporating method followed with ultrasonication. During evaporation process, the ibuprofen concentration in emulsion droplets was increased leading to a drug supersaturation but did not immediately recrystallize because of low glass transition temperature (Tg) of ibuprofen. The contact angle of the internal phase on ibuprofen was apparently lower than that of the external phase at all times of evaporation, indicating that the ibuprofen crystals were preferentially wetted by the internal phase than the external phase. From calculated dewetting value ibuprofen crystallization occurred in the droplet. Crystallization of the drug was initiated with external mechanical force, and the particle size of the drug was larger due to Ostwald ripening. Cavitation force from ultrasonication minimized the ibuprofen crystals to the nanoscale. Particle size and zeta potential of formulated ibuprofen nanosuspension were 330.87±51.49 nm and −31.1±1.6 mV, respectively, and exhibited a fast dissolution. Therefore, the combination of eutectic emulsion solvent evaporation method with ultrasonication was favorable for fabricating an ibuprofen nanosuspension, and the transformation mechanism was attained successfully. PMID:27366064

Transformation of eutectic emulsion to nanosuspension fabricating with solvent evaporation and ultrasonication technique.

PubMed

Phaechamud, Thawatchai; Tuntarawongsa, Sarun

2016-01-01

Eutectic solvent can solubilize high amount of some therapeutic compounds. Volatile eutectic solvent is interesting to be used as solvent in the preparation of nanosuspension with emulsion solvent evaporation technique. The mechanism of transformation from the eutectic emulsion to nanosuspension was investigated in this study. The 30% w/w ibuprofen eutectic solution was used as the internal phase, and the external phase is composed of Tween 80 as emulsifier. Ibuprofen nanosuspension was prepared by eutectic emulsion solvent evaporating method followed with ultrasonication. During evaporation process, the ibuprofen concentration in emulsion droplets was increased leading to a drug supersaturation but did not immediately recrystallize because of low glass transition temperature (T g) of ibuprofen. The contact angle of the internal phase on ibuprofen was apparently lower than that of the external phase at all times of evaporation, indicating that the ibuprofen crystals were preferentially wetted by the internal phase than the external phase. From calculated dewetting value ibuprofen crystallization occurred in the droplet. Crystallization of the drug was initiated with external mechanical force, and the particle size of the drug was larger due to Ostwald ripening. Cavitation force from ultrasonication minimized the ibuprofen crystals to the nanoscale. Particle size and zeta potential of formulated ibuprofen nanosuspension were 330.87±51.49 nm and -31.1±1.6 mV, respectively, and exhibited a fast dissolution. Therefore, the combination of eutectic emulsion solvent evaporation method with ultrasonication was favorable for fabricating an ibuprofen nanosuspension, and the transformation mechanism was attained successfully.

Stable colloids in molten inorganic salts

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

Zhang, Hao; Dasbiswas, Kinjal; Ludwig, Nicholas B.

2017-02-15

A colloidal solution is a homogeneous dispersion of particles or droplets of one phase (solute) in a second, typically liquid, phase (solvent). Colloids are ubiquitous in biological, chemical and technological processes1, 2, homogenizing highly dissimilar constituents. To stabilize a colloidal system against coalescence and aggregation, the surface of each solute particle is engineered to impose repulsive forces strong enough to overpower van der Waals attraction and keep the particles separated from each other2. Electrostatic stabilization3, 4 of charged solutes works well in solvents with high dielectric constants, such as water (dielectric constant of 80). In contrast, colloidal stabilization in solventsmore » with low polarity, such as hexane (dielectric constant of about 2), can be achieved by decorating the surface of each particle of the solute with molecules (surfactants) containing flexible, brush-like chains2, 5. Here we report a class of colloidal systems in which solute particles (including metals, semiconductors and magnetic materials) form stable colloids in various molten inorganic salts. The stability of such colloids cannot be explained by traditional electrostatic and steric mechanisms. Screening of many solute–solvent combinations shows that colloidal stability can be traced to the strength of chemical bonding at the solute–solvent interface. Theoretical analysis and molecular dynamics modelling suggest that a layer of surface-bound solvent ions produces long-ranged charge-density oscillations in the molten salt around solute particles, preventing their aggregation. Colloids composed of inorganic particles in inorganic melts offer opportunities for introducing colloidal techniques to solid-state science and engineering applications.« less

Physicochemical properties/descriptors governing the solubility and partitioning of chemicals in water-solvent-gas systems. Part 1. Partitioning between octanol and air.

PubMed

Raevsky, O A; Grigor'ev, V J; Raevskaja, O E; Schaper, K-J

2006-06-01

QSPR analyses of a data set containing experimental partition coefficients in the three systems octanol-water, water-gas, and octanol-gas for 98 chemicals have shown that it is possible to calculate any partition coefficient in the system 'gas phase/octanol/water' by three different approaches: (1) from experimental partition coefficients obtained in the corresponding two other subsystems. However, in many cases these data may not be available. Therefore, a solution may be approached (2), a traditional QSPR analysis based on e.g. HYBOT descriptors (hydrogen bond acceptor and donor factors, SigmaCa and SigmaCd, together with polarisability alpha, a steric bulk effect descriptor) and supplemented with substructural indicator variables. (3) A very promising approach which is a combination of the similarity concept and QSPR based on HYBOT descriptors. In this approach observed partition coefficients of structurally nearest neighbours of a compound-of-interest are used. In addition, contributions arising from differences in alpha, SigmaCa, and SigmaCd values between the compound-of-interest and its nearest neighbour(s), respectively, are considered. In this investigation highly significant relationships were obtained by approaches (1) and (3) for the octanol/gas phase partition coefficient (log Log).

Supercritical fluid reverse micelle separation

DOEpatents

Fulton, John L.; Smith, Richard D.

1993-01-01

A method of separating solute material from a polar fluid in a first polar fluid phase is provided. The method comprises combining a polar fluid, a second fluid that is a gas at standard temperature and pressure and has a critical density, and a surfactant. The solute material is dissolved in the polar fluid to define the first polar fluid phase. The combined polar and second fluids, surfactant, and solute material dissolved in the polar fluid is maintained under near critical or supercritical temperature and pressure conditions such that the density of the second fluid exceeds the critical density thereof. In this way, a reverse micelle system defining a reverse micelle solvent is formed which comprises a continuous phase in the second fluid and a plurality of reverse micelles dispersed in the continuous phase. The solute material is dissolved in the polar fluid and is in chemical equilibrium with the reverse micelles. The first polar fluid phase and the continuous phase are immiscible. The reverse micelles each comprise a dynamic aggregate of surfactant molecules surrounding a core of the polar fluid. The reverse micelle solvent has a polar fluid-to-surfactant molar ratio W, which can vary over a range having a maximum ratio W.sub.o that determines the maximum size of the reverse micelles. The maximum ratio W.sub.o of the reverse micelle solvent is then varied, and the solute material from the first polar fluid phase is transported into the reverse micelles in the continuous phase at an extraction efficiency determined by the critical or supercritical conditions.

Supercritical fluid reverse micelle separation

DOEpatents

Fulton, J.L.; Smith, R.D.

1993-11-30

A method of separating solute material from a polar fluid in a first polar fluid phase is provided. The method comprises combining a polar fluid, a second fluid that is a gas at standard temperature and pressure and has a critical density, and a surfactant. The solute material is dissolved in the polar fluid to define the first polar fluid phase. The combined polar and second fluids, surfactant, and solute material dissolved in the polar fluid is maintained under near critical or supercritical temperature and pressure conditions such that the density of the second fluid exceeds the critical density thereof. In this way, a reverse micelle system defining a reverse micelle solvent is formed which comprises a continuous phase in the second fluid and a plurality of reverse micelles dispersed in the continuous phase. The solute material is dissolved in the polar fluid and is in chemical equilibrium with the reverse micelles. The first polar fluid phase and the continuous phase are immiscible. The reverse micelles each comprise a dynamic aggregate of surfactant molecules surrounding a core of the polar fluid. The reverse micelle solvent has a polar fluid-to-surfactant molar ratio W, which can vary over a range having a maximum ratio W[sub o] that determines the maximum size of the reverse micelles. The maximum ratio W[sub o] of the reverse micelle solvent is then varied, and the solute material from the first polar fluid phase is transported into the reverse micelles in the continuous phase at an extraction efficiency determined by the critical or supercritical conditions. 27 figures.

Experimental and theoretical aspects of studying themodynamics and mass transport in polymer-solvent systems

NASA Astrophysics Data System (ADS)

Davis, Peter Kennedy

Mass transport and thermodynamics in polymer-solvent systems are two key areas of importance to the polymer industry. Numerous processes including polymerization reactors, membrane separations, foam production, devolatilization processes, film and coating drying, supercritical extractions, drug delivery, and even nano-technology require fundamental phase equilibria and diffusion information. Although such information is vital in equipment design and optimization, acquisition and modeling of these data are still in the research and development stages. This thesis is rather diverse as it addresses many realms of this broad research area. From high pressure to low pressure, experimental to theoretical, and infinite dilution to finite concentration, the thesis covers a wide range of topics that are of current importance to the industrial and academic polymer community. Chapter 1 discusses advances in the development of a new volumetric sorption pressure decay technique to make phase equilibrium and diffusion measurements in severe temperature-pressure environments. Chapter 2 provides the derivations and results of a new completely predictive Group Contribution Lattice Fluid Equation of State for multi-component polymer-solvent systems. The remaining four chapters demonstrate advances in the modeling of inverse gas chromatography (IGC) experiments. IGC has been used extensively of the last 50 years to make low pressure sorption and diffusion measurements at infinitely dilute and finite solvent concentrations. Chapter 3 proposes a new IGC experiment capable of obtaining ternary vapor-liquid equilibria in polymer-solvent-solvent systems. Also in that chapter, an extensive derivation is provided for a continuum model capable of describing the results of such an experiment. Chapter 4 presents new data collected on a packed column IGC experiment and a new model that can be used with those experimental data to obtain diffusion and partition coefficients. Chapter 5 addresses a rather controversial topic about IGC experiments near the polymer glass transition temperature. Using a new IGC model capable of describing both bulk absorption and surface adsorption, IGC behavior around the glass transition was able to be better understood. Finally, Chapter 6 presents an IGC model that can be used to separate bulk effects from surface effects in capillary column IGC experiments.

Morphological control in polymer solar cells using low-boiling-point solvent additives

NASA Astrophysics Data System (ADS)

Mahadevapuram, Rakesh C.

In the global search for clean, renewable energy sources, organic photovoltaics (OPVs) have recently been given much attention. Popular modern-day OPVs are made from solution-processible, carbon-based polymers (e.g. the model poly(3-hexylthiophene) that are intimately blended with fullerene derivatives (e.g. [6,6]-phenyl-C71-butyric acid methyl ester) to form what is known as the dispersed bulk-heterojunction (BHJ). This BHJ architecture has produced some of the most efficient OPVs to date, with reports closing in on 10% power conversion efficiency. To push efficiencies further into double digits, many groups have identified the BHJ nanomorphology---that is, the phase separations and grain sizes within the polymer: fullerene composite---as a key aspect in need of control and improvement. As a result, many methods, including thermal annealing, slow-drying (solvent) annealing, vapor annealing, and solvent additives, have been developed and studied to promote BHJ self-organization. Processing organic photovoltaic (OPV) blend solutions with high-boiling-point solvent additives has recently been used for morphological control in BHJ OPV cells. Here we show that even low-boiling-point solvents can be effective additives. When P3HT:PCBM OPV cells were processed with a low-boiling-point solvent tetrahydrafuran as an additive in parent solvent o-dichlorobenzene, charge extraction increased leading to fill factors as high as 69.5%, without low work-function cathodes, electrode buffer layers or thermal treatment. This was attributed to PCBM demixing from P3HT domains and better vertical phase separation, as indicated by photoluminescence lifetimes, hole mobilities, and shunt leakage currents. Dependence on solvent parameters and applicability beyond P3HT system was also investigated.

Method for determining asphaltene stability of a hydrocarbon-containing material

DOEpatents

Schabron, John F; Rovani, Jr., Joseph F

2013-02-05

A method for determining asphaltene stability in a hydrocarbon-containing material having solvated asphaltenes therein is disclosed. In at least one embodiment, it involves the steps of: (a) precipitating an amount of the asphaltenes from a liquid sample of the hydrocarbon-containing material with an alkane mobile phase solvent in a column; (b) dissolving a first amount and a second amount of the precipitated asphaltenes by changing the alkane mobile phase solvent to a final mobile phase solvent having a solubility parameter that is higher than the alkane mobile phase solvent; (c) monitoring the concentration of eluted fractions from the column; (d) creating a solubility profile of the dissolved asphaltenes in the hydrocarbon-containing material; and (e) determining one or more asphaltene stability parameters of the hydrocarbon-containing material.

Optimization of the emulsification and solvent displacement method for the preparation of solid lipid nanoparticles.

PubMed

Noriega-Peláez, Eddy Kei; Mendoza-Muñoz, Néstor; Ganem-Quintanar, Adriana; Quintanar-Guerrero, David

2011-02-01

The essential aim of this article is to prepare solid lipid nanoparticles (SLNs) by emulsification and solvent displacement method and to determine the best process conditions to obtain submicron particles. The emulsification and solvent displacement method is a modification of the well-known emulsification-diffusion method, but without dilution of the system. The extraction of the partially water-miscible solvent from the emulsion globules is carried out under reduced pressure, which causes the diffusion of the solvent toward the external phase, with subsequent lipid aggregation in particles whose size will depend on the process conditions. The critical variables affecting the process, such as stirring rate, the proportion of phases in the emulsion, and the amount of stabilizer and lipid, were evaluated and optimized. By this method, it was possible to obtain a high yield of solids in the dispersion for the lipids evaluated (Compritol(®) ATO 888, Geleol(®), Gelucire(®) 44/14, and stearic acid). SLNs of up to ∼20 mg/mL were obtained for all lipids evaluated. A marked reduction in size, between 500 and 2500 rpm, was seen, and a transition from micro- to nanometric size was observed. The smaller particle sizes obtained were 113 nm for Compritol(®) ATO 888, 70 nm for Gelucire(®) 44/14, 210 nm for Geleol(®), and 527 nm for stearic acid, using a rotor-stator homogenizer (Ultra-Turrax(®)) at 16,000 rpm. The best phase ratio (organic/aqueous) was 1 : 2. The process proposed in this study is a new alternative to prepare SLNs with technological potential.

Method of analysis of polymerizable monomeric species in a complex mixture

DOEpatents

Hermes, Robert E

2014-03-18

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

Porous Polyimide Membranes Prepared by Wet Phase Inversion for Use in Low Dielectric Applications

PubMed Central

Kim, Soohyun; Jang, Keon-Soo; Choi, Hee-Dok; Choi, Seung-Hoon; Kwon, Seong-Ji; Kim, Il-Doo; Lim, Jung Ah; Hong, Jae-Min

2013-01-01

A wet phase inversion process of polyamic acid (PAA) allowed fabrication of a porous membrane of polyimide (PI) with the combination of a low dielectric constant (1.7) and reasonable mechanical properties (Tensile strain: 8.04%, toughness: 3.4 MJ/m3, tensile stress: 39.17 MPa, and young modulus: 1.13 GPa), with further thermal imidization process of PAA. PAA was simply synthesized from purified pyromellitic dianhydride (PMDA) and 4,4-oxydianiline (ODA) in two different reaction solvents such as γ-butyrolactone (GBL) and N-methyl-2-pyrrolidinone (NMP), which produce Mw/PDI of 630,000/1.45 and 280,000/2.0, respectively. The porous PAA membrane was fabricated by the wet phase inversion process based on a solvent/non-solvent system via tailored composition between GBL and NMP. The porosity of PI, indicative of a low electric constant, decreased with increasing concentration of GBL, which was caused by sponge-like formation. However, due to interplay between the low electric constant (structural formation) and the mechanical properties, GBL was employed for further exploration, using toluene and acetone vs. DI-water as a coagulation media. Non-solvents influenced determination of the PAA membrane size and porosity. With this approach, insight into the interplay between dielectric properties and mechanical properties will inform a wide range of potential low-k material applications. PMID:23615465

Preparative isolation of a cytotoxic principle of a forest mushroom Suillus luteus by sodium dodecyl sulfate based "salting-in" countercurrent chromatography.

PubMed

Yang, Zhi; Hu, Xueqian; Wu, Shihua

2016-02-01

In the course of screening new anticancer natural products, an edible forest mushroom Suillus luteus (L. Ex Franch). Gray was found to have potent cytotoxicity against several human cancer cells. However, the lipophilic sample made some countercurrent chromatography solvent systems emulsify, which caused difficulties in the separation of its cytotoxic components. Here, we found that the addition of an organic salt sodium dodecyl sulfate could efficiently shorten the settling time of the mushroom sample solutions by eliminating the emulsification of two-phase solvent systems. Moreover, we found that sodium dodecyl sulfate could play a new "salting-in" role and made the partition coefficients of the solutes decrease with the increased concentrations. Thus, a sodium dodecyl sulfate based salting-in countercurrent chromatography method has been successfully established for the first time for preparative isolation of a cytotoxic principle of the mushroom. The active component was identified as isosuillin. Whole results indicated that sodium dodecyl sulfate could be used as an efficient salting-in reagent for two-phase solvent system selection and targeted countercurrent chromatography isolation. It is very useful for current natural products isolation and drug discovery. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Selection of operating parameters on the basis of hydrodynamics in centrifugal partition chromatography for the purification of nybomycin derivatives.

PubMed

Adelmann, S; Baldhoff, T; Koepcke, B; Schembecker, G

2013-01-25

The selection of solvent systems in centrifugal partition chromatography (CPC) is the most critical point in setting up a separation. Therefore, lots of research was done on the topic in the last decades. But the selection of suitable operating parameters (mobile phase flow rate, rotational speed and mode of operation) with respect to hydrodynamics and pressure drop limit in CPC is still mainly driven by experience of the chromatographer. In this work we used hydrodynamic analysis for the prediction of most suitable operating parameters. After selection of different solvent systems with respect to partition coefficients for the target compound the hydrodynamics were visualized. Based on flow pattern and retention the operating parameters were selected for the purification runs of nybomycin derivatives that were carried out with a 200 ml FCPC(®) rotor. The results have proven that the selection of optimized operating parameters by analysis of hydrodynamics only is possible. As the hydrodynamics are predictable by the physical properties of the solvent system the optimized operating parameters can be estimated, too. Additionally, we found that dispersion and especially retention are improved if the less viscous phase is mobile. Crown Copyright © 2012. Published by Elsevier B.V. All rights reserved.

Vapor-phase interactions and diffusion of organic solvents in the unsaturated zone

USGS Publications Warehouse

Roy, W.R.; Griffin, R.A.

1990-01-01

This article presents an analysis of the interactions and static movement of 37 organic solvents as vapors through the unsaturated soil zone. The physicochemical interactions of the organic vapors with unsaturated soil materials were emphasized with focus on diffusive, and adsorptive interactions. Fick's Law and porous media diffusion coefficients for most of the solvent vapors were either compiled or estimated; coefficients were not available for some of the fluorinated solvents. The adsorption of some of the solvent vapors by silica was concluded to be due to hydrogen bond formation with surface silanol groups. Heats of adsorption data for different adsorbents were also compiled. There were very few data on the adsorption of these solvent vapors by soils, but it appears that the magnitude of adsorption of nonpolar solvents is reduced as the relative humidity of the vapor-solid system is increased. Consequently, the interaction of the vapors may then separated into two processes; (1) gas-water partitioning described by Henry's Law constants, and (2) solid-water adsorption coefficients which may be estimated from liquid-solid partition coefficients (Kd values). ?? 1990 Springer-Verlag New York Inc.

Development of continuous dispersive liquid-liquid microextraction performed in home-made device for extraction and preconcentration of aryloxyphenoxy-propionate herbicides from aqueous samples followed by gas chromatography-flame ionization detection.

PubMed

Farajzadeh, Mir Ali; Mohebbi, Ali; Feriduni, Behruz

2016-05-12

In this study, a rapid, simple, and efficient sample preparation method based on continuous dispersive liquid-liquid microextraction has been developed for the extraction and preconcentration of aryloxyphenoxy-propionate herbicides from aqueous samples prior to their analysis by gas chromatography-flame ionization detection. In this method, two parallel glass tubes with different diameters are connected with a teflon stopcock and used as an extraction device. A mixture of disperser and extraction solvents is transferred into one side (narrow tube) of the extraction device and an aqueous phase containing the analytes is filled into the other side (wide tube). Then the stopcock is opened and the mixture of disperser and extraction solvents mixes with the aqueous phase. By this action, the extraction solvent is dispersed continuously as fine droplets into the aqueous sample and the target analytes are extracted into the fine droplets of the extraction solvent. The fine droplets move up through the aqueous phase due to its low density compared to aqueous phase and collect on the surface of the aqueous phase as an organic layer. Finally an aliquot of the organic phase is removed and injected into the separation system for analysis. Several parameters that can affect extraction efficiency including type and volume of extraction and disperser solvents, sample pH, and ionic strength were investigated and optimized. Under the optimum extraction conditions, the extraction recoveries and enrichment factors ranged from 49 to 74% and 1633 to 2466, respectively. Relative standard deviations were in the ranges of 3-6% (n = 6, C = 30 μg L(-1)) for intra-day and 4-7% (n = 4, C = 30 μg L(-1)) for inter-day precisions. The limits of detection were in the range of 0.20-0.86 μg L(-1). Finally the proposed method was successfully applied to determine the target herbicides in fruit juice and vegetable samples. Copyright © 2016 Elsevier B.V. All rights reserved.

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.

Biodiesel production from ethanolysis of palm oil using deep eutectic solvent (DES) as co-solvent

NASA Astrophysics Data System (ADS)

Manurung, R.; Winarta, A.; Taslim; Indra, L.

2017-06-01

Biodiesel produced from ethanolysis is more renewable and have better properties (higher oxidation stability, lower cloud and pour point) compared to methanolysis, but it has a disadvantage such as complicated purification. To improve ethanolysis process, deep eutectic solvent (DES) can be prepared from choline chloride and glycerol and used as co-solvent in ethanolysis. The deep eutectic solvent is formed from a quaternary ammonium salt (choline chloride) and a hydrogen bond donor (Glycerol), it is a non-toxic, biodegradable solvent compared to a conventional volatile organic solvent such as hexane. The deep eutectic solvent is prepared by mixing choline chloride and glycerol with molar ratio 1:2 at temperature 80 °C, stirring speed 300 rpm for 1 hour. The DES is characterized by its density and viscosity. The ethanolysis is performed at a reaction temperature of 70 °C, ethanol to oil molar ratio of 9:1, potassium hydroxide as catalyst concentration of 1.2 wt. DES as co-solvent with concentration 0.5 to 3 wt. stirring speed 400 rpm, and a reaction time 1 hour. The obtained biodiesel is then characterized by its density, viscosity, and ester content. The oil - ethanol phase condition is observed in the reaction tube. The oil - ethanol phase with DES tends to form meniscus compared to without DES, showed that oil and ethanol become more slightly miscible, which favors the reaction. Using DES as co-solvent in ethanolysis showed increasing in yield and easier purification. The esters properties meet the international standards ASTM D6751, with the highest yield achieved 83,67 with 99,77 conversion at DES concentration 2 . Increasing DES concentration above 2 in ethanolysis decrease the conversion and yield, because of the excessive glycerol in the systems makes the reaction equilibrium moves to the reactant side.

Direct Coal -to-Liquids (CTL) for Jet Fuel Using Biomass-Derived Solvents

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

Chauhan, Satya P.; Garbark, Daniel B.; Taha, Rachid

Battelle has demonstrated a novel and potentially breakthrough technology for a direct coal-to-liquids (CTL) process for producing jet fuel using biomass-derived coal solvents (bio-solvents). The Battelle process offers a significant reduction in capital and operating costs and a substantial reduction in greenhouse gas (GHG) emissions, without requiring carbon capture and storage (CCS). The results of the project are the advancement of three steps of the hybrid coal/biomass-to-jet fuel process to the technology readiness level (TRL) of 5. The project objectives were achieved over two phases. In Phase 1, all three major process steps were explored and refined at bench-scale, including:more » (1) biomass conversion to high hydrogen-donor bio-solvent; (2) coal dissolution in biomass-derived bio-solvent, without requiring molecular H 2, to produce a synthetic crude (syncrude); and (3) two-stage catalytic hydrotreating/hydrogenation of syncrude to jet fuel and other distillates. In Phase 2, all three subsystems of the CTL process were scaled up to a pre-pilot scale, and an economic analysis was carried out. A total of over 40 bio-solvents were identified and prepared. The most unique attribute of Battelle’s bio-solvents is their ability to provide much-needed hydrogen to liquefy coal and thus increase its hydrogen content so much that the resulting syncrude is liquid at room temperature. Based on the laboratory-scale testing with bituminous coals from Ohio and West Virginia, a total of 12 novel bio-solvent met the goal of greater than 80% coal solubility, with 8 bio-solvents being as good as or better than a well-known but expensive hydrogen-donor solvent, tetralin. The Battelle CTL process was then scaled up to 1 ton/day (1TPD) at a pre-pilot facility operated in Morgantown, WV. These tests were conducted, in part, to produce enough material for syncrude-upgrading testing. To convert the Battelle-CTL syncrude into a form suitable as a blending stock for jet turbine fuel, a two-step catalytic upgrading process was developed at laboratory scale and then demonstrated at pre-pilot scale facility in Pittsburg, PA. Several drums of distillate products were produced, which were then distilled into unblended (neat) synthetic jet fuel and diesel products for a detailed characterization. Based on a detailed characterization of the synthetic jet fuel, a 20% synthetic, 80% commercial jet fuel blend was prepared, which met all specifications. An analysis of the synthetic diesel product showed that it has the promise of being a drop-in fuel as super-low (less than 15 ppm)-sulfur diesel fuel. A detailed economic analysis showed that the Battelle liquefaction process is economical at between 1000 metric tons/day (MT/day) and 2000 MT/day. The unit capital cost for Battelle CTL process for making jet fuel is 50K USD/daily bbl compared to 151K USD/daily bbl for indirect CTL, based on 2011 dollars. The jet-fuel selling cost at the refinery, including a 12% capital cost factor (which included profit), for the Battelle CTL process is 61USD/bbl (1.45 USD/gallon). This is competitive with crude oil price of 48 USD/bbl. At the same time, the GHG emissions of 3.56 MT CO 2/MT fuel were lower than the GHG emissions of 3.79 MT CO 2/MTfuel for petroleum-based fuels and 7.77 MT CO 2/MT fuel for indirect CTL. Thus, the use of bio-solvents completely eliminates the need for carbon capture in the case of Battelle CTL process. The superior economics and low GHG emissions for the Battelle CTL process has thus sparked worldwide interest and some potential commercialization opportunities are emerging.« less

Biodegradation and Sorption of Organic Solvents and Hydrocarbon Fuel Constituents in Subsurface Environments

DTIC Science & Technology

1988-03-01

soluticn-phase concentration changes is the iack of precision when sorption is low. In many of these experiments, because of low soil solution ratios less...effect of varying soil solution ratio was evAluated for Sample 6 by performing concurrent isotherm experiments at three different ratios. For this sorbent

A green deep eutectic solvent-based aqueous two-phase system for protein extracting.

PubMed

Xu, Kaijia; Wang, Yuzhi; Huang, Yanhua; Li, Na; Wen, Qian

2015-03-15

As a new type of green solvent, deep eutectic solvent (DES) has been applied for the extraction of proteins with an aqueous two-phase system (ATPS) in this work. Four kinds of choline chloride (ChCl)-based DESs were synthesized to extract bovine serum albumin (BSA), and ChCl-glycerol was selected as the suitable extraction solvent. Single factor experiments have been done to investigate the effects of the extraction process, including the amount of DES, the concentration of salt, the mass of protein, the shaking time, the temperature and PH value. Experimental results show 98.16% of the BSA could be extracted into the DES-rich phase in a single-step extraction under the optimized conditions. A high extraction efficiency of 94.36% was achieved, while the conditions were applied to the extraction of trypsin (Try). Precision, repeatability and stability experiments were studied and the relative standard deviations (RSD) of the extraction efficiency were 0.4246% (n=3), 1.6057% (n=3) and 1.6132% (n=3), respectively. Conformation of BSA was not changed during the extraction process according to the investigation of UV-vis spectra, FT-IR spectra and CD spectra of BSA. The conductivity, dynamic light scattering (DLS) and transmission electron microscopy (TEM) were used to explore the mechanism of the extraction. It turned out that the formation of DES-protein aggregates play a significant role in the separation process. All the results suggest that ChCl-based DES-ATPS are supposed to have the potential to provide new possibilities in the separation of proteins. Copyright © 2015 Elsevier B.V. All rights reserved.

Visualization of Two-Phase Fluid Distribution Using Laser Induced Exciplex Fluorescence

NASA Astrophysics Data System (ADS)

Kim, J. U.; Darrow, J.; Schock, H.; Golding, B.; Nocera, D.; Keller, P.

1998-03-01

Laser-induced exciplex (excited state complex) fluorescence has been used to generate two-dimensional images of dispersed liquid and vapor phases with spectrally resolved two-color emissions. In this method, the vapor phase is tagged by the monomer fluorescence while the liquid phase is tracked by the exciplex fluorescence. A new exciplex visualization system consisting of DMA and 1,4,6-TMN in an isooctane solvent was developed.(J.U. Kim et al., Chem. Phys. Lett. 267, 323-328 (1997)) The direct ca

The Denaturation Transition of DNA in Mixed Solvents

PubMed Central

Hammouda, Boualem; Worcester, David

2006-01-01

The helix-to-coil denaturation transition in DNA has been investigated in mixed solvents at high concentration using ultraviolet light absorption spectroscopy and small-angle neutron scattering. Two solvents have been used: water and ethylene glycol. The “melting” transition temperature was found to be 94°C for 4% mass fraction DNA/d-water and 38°C for 4% mass fraction DNA/d-ethylene glycol. The DNA melting transition temperature was found to vary linearly with the solvent fraction in the mixed solvents case. Deuterated solvents (d-water and d-ethylene glycol) were used to enhance the small-angle neutron scattering signal and 0.1M NaCl (or 0.0058 g/g mass fraction) salt concentration was added to screen charge interactions in all cases. DNA structural information was obtained by small-angle neutron scattering, including a correlation length characteristic of the inter-distance between the hydrogen-containing (desoxyribose sugar-amine base) groups. This correlation length was found to increase from 8.5 to 12.3 Å across the melting transition. Ethylene glycol and water mixed solvents were found to mix randomly in the solvation region in the helix phase, but nonideal solvent mixing was found in the melted coil phase. In the coil phase, solvent mixtures are more effective solvating agents than either of the individual solvents. Once melted, DNA coils behave like swollen water-soluble synthetic polymer chains. PMID:16815902

Application of a biphasic test for characterization of in vitro drug release of immediate release formulations of celecoxib and its relevance to in vivo absorption.

PubMed

Shi, Yi; Gao, Ping; Gong, Yuchuan; Ping, Haili

2010-10-04

A biphasic in vitro test method was used to examine release profiles of a poorly soluble model drug, celecoxib (CEB), from its immediate release formulations. Three formulations of CEB were investigated in this study, including a commercial Celebrex capsule, a solution formulation (containing cosolvent and surfactant) and a supersaturatable self-emulsifying drug delivery system (S-SEDDS). The biphasic test system consisted of an aqueous buffer and a water-immiscible organic solvent (e.g., octanol) with the use of both USP II and IV apparatuses. The aqueous phase provided a nonsink dissolution medium for CEB, while the octanol phase acted as a sink for CEB partitioning. For comparison, CEB concentration-time profiles of these formulations in the aqueous medium under either a sink condition or a nonsink condition were also explored. CEB release profiles of these formulations observed in the aqueous medium from either the sink condition test, the nonsink condition test, or the biphasic test have little relevance to the pharmacokinetic observations (e.g., AUC, C(max)) in human subjects. In contrast, a rank order correlation among the three CEB formulations is obtained between the in vitro AUC values of CEB from the octanol phase up to t = 2 h and the in vivo mean AUC (or C(max)) values. As the biphasic test permits a rapid removal of drug from the aqueous phase by partitioning into the organic phase, the amount of drug in the organic phase represents the amount of drug accumulated in systemic circulation in vivo. This hypothesis provides the scientific rationale for the rank order relationship among these CEB formulations between their CEB concentrations in the organic phase and the relative AUC or C(max). In addition, the biphasic test method permits differentiation and discrimination of key attributes among the three different CEB formulations. This work demonstrates that the biphasic in vitro test method appears to be useful as a tool in evaluating performance of formulations of poorly water-soluble drugs and to provide potential for establishing an in vitro-in vivo relationship.

Fluoro-alcohol phase modifiers and process for cesium solvent extraction

DOEpatents

Bonnesen, Peter V.; Moyer, Bruce A.; Sachleben, Richard A.

2003-05-20

The invention relates to a class of phenoxy fluoro-alcohols, their preparation, and their use as phase modifiers and solvating agents in a solvent composition for the extraction of cesium from alkaline solutions. These phenoxy fluoro-alcohols comply with the formula: ##STR1## in which n=2 to 4; X represents a hydrogen or a fluorine atom, and R.sup.2 -R.sup.6 are hydrogen or alkyl substituents. These phenoxy fluoro-alcohol phase modifiers are a necessary component to a robust solvent composition and process useful for the removal of radioactive cesium from alkaline nuclear waste streams. The fluoro-alcohols can also be used in solvents designed to extract other cesium from acidic or neutral solutions.

Journal of Chemical Education: Software.

ERIC Educational Resources Information Center

Journal of Chemical Education, 1988

1988-01-01

Describes a chemistry software program that emulates a modern binary gradient HPLC system with reversed phase column behavior. Allows for solvent selection, adjustment of gradient program, column selection, detectory selection, handling of computer sample data, and sample preparation. (MVL)

Far-ultraviolet absorbance detection of sugars and peptides by high-performance liquid chromatography.

PubMed

Uchiho, Yuichi; Goto, Yusuke; Kamahori, Masao; Aota, Toshimichi; Morisaki, Atsuki; Hosen, Yusuke; Koda, Kimiyoshi

2015-12-11

A far-ultraviolet (FUV)-absorbance detector with a transmission flow cell was developed and applied to detect absorbance of sugars and peptides by HPLC. The main inherent limitation of FUV-absorbance detection is the strong absorptions of solvents and atmospheric oxygen in the optical system as well as dissolved oxygen in the solvent. High absorptivity of the solvent and oxygen decreases transmission-light intensity in the flow cell and hinders the absorbance measurement. To solve the above drawbacks, the transmission-light intensity in the flow cell was increased by introducing a new optical system and a nitrogen-purging unit to remove the atmospheric oxygen. The optical system has a photodiode for detecting the reference light at a position of the minus-first-order diffracted light. In addition, acetonitrile and water were selected as usable solvents because of their low absorptivity in the FUV region. As a result of these implementations, the detectable wavelength of the FUV-absorbance detector (with a flow cell having an effective optical path length of 0.5mm) can be extended down to 175nm. Three sugars (glucose, fructose, and sucrose) were successfully detected with the FUV-absorbance detector. These detection results reveal that the absorption peak of sugar in liquid phase lies at around 178nm. The detection limit (S/N=3) in absorbance with a 0.5-mm flow cell at 180nm was 21μAU, which corresponds to 33, 60 and 60μM (198, 360, and 360pmol) for fructose, glucose, and sucrose, respectively. Also, the peptide Met-enkephalin could be detected with a high sensitivity at 190nm. The estimated detection limit (S/N=3) for Met-enkephalin is 29nM (0.29pmol), which is eight times lower than that at 220nm. Copyright © 2015 Elsevier B.V. All rights reserved.

Advanced liquefaction using coal swelling and catalyst dispersion techniques. Quarterly progress report, July--September 1993

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

Curtis, C.W.; Gutterman, C.; Chander, S.

The overall objective of this project is to develop a new approach for the direct liquefaction of coal to produce an all-distillate product slate at a sizable cost reduction over current technology. The approach integrates coal selection, pretreatment, coal swelling with catalyst impregnation, liquefaction, product recovery with characterization, alternate bottoms processing, and carrying out a technical assessment including an economic evaluation. The primary coal of this program, Black Thunder subbituminous coal, can be effectively beneficiated to about 3.5 wt % ash using aqueous sulfurous acid pretreatment. This treated coal can be further beneficiated to about 2 wt % ash usingmore » commercially available procedures. All three coals used in this study (Black Thunder, Burning Star bituminous, and Martin Lake lignite) are effectively swelled by a number of solvents. The most effective solvents are those having hetero-functionality. laboratory- and bench-scale liquefaction experimentation is underway using swelled and catalyst impregnated coal samples. Higher coal conversions were observed for the SO{sub 2}-treated subbituminous coal than the raw coal, regardless of catalyst type. Conversions of swelled coal were highest when Molyvan L, molybdenum naphthenate, and nickel octoate, respectively, were added to the liquefaction solvent. The study of bottoms processing consists of combining the ASCOT process which consists of coupling solvent deasphalting with delayed coking to maximize the production of coal-derived liquids while rejecting solids within the coke drum. The asphalt production phase has been completed; representative product has been evaluated. The solvent system for the deasphalting process has been established. Two ASCOT tests produced overall liquid yields (63.3 wt % and 61.5 wt %) that exceeded the combined liquid yields from the vacuum tower and ROSE process.« less

In Situ Miniaturised Solid Phase Extraction (m-SPE) for Organic Pollutants in Seawater Samples

PubMed Central

Abaroa-Pérez, B.; Sánchez-Almeida, G.; Hernández-Brito, J. J.

2018-01-01

Solid phase extraction (SPE) is a consolidated technique for determining pollutants in seawater samples. The current tendency is to miniaturise systems that extract and determine pollutants in the environment, reducing the use of organic solvents, while maintaining the quality in the extraction and preconcentration. On the other hand, there is a need to develop new extraction systems that can be fitted to in situ continual monitoring buoys, especially for the marine environment. This work has developed a first model of a low-pressure micro-SPE (m-SPE) for persistent organic pollutants (POPs) that can be simply applied to in situ monitoring in the marine environment. This system reduces the volumes of sample and solvents required in the laboratory in comparison with conventional SPE. In the future, it could be used in automated or robotic systems in marine technologies such as marine gliders and oceanographic buoys. This system has been optimised and validated to determine polycyclic aromatic hydrocarbons (PAH) in seawater samples, but it could also be applied to other kinds of persistent organic pollutants (POPs) and emerging pollutants. PMID:29805837

Competing Intramolecular vs. Intermolecular Hydrogen Bonds in Solution

PubMed Central

Nagy, Peter I.

2014-01-01

A hydrogen bond for a local-minimum-energy structure can be identified according to the definition of the International Union of Pure and Applied Chemistry (IUPAC recommendation 2011) or by finding a special bond critical point on the density map of the structure in the framework of the atoms-in-molecules theory. Nonetheless, a given structural conformation may be simply favored by electrostatic interactions. The present review surveys the in-solution competition of the conformations with intramolecular vs. intermolecular hydrogen bonds for different types of small organic molecules. In their most stable gas-phase structure, an intramolecular hydrogen bond is possible. In a protic solution, the intramolecular hydrogen bond may disrupt in favor of two solute-solvent intermolecular hydrogen bonds. The balance of the increased internal energy and the stabilizing effect of the solute-solvent interactions regulates the new conformer composition in the liquid phase. The review additionally considers the solvent effects on the stability of simple dimeric systems as revealed from molecular dynamics simulations or on the basis of the calculated potential of mean force curves. Finally, studies of the solvent effects on the type of the intermolecular hydrogen bond (neutral or ionic) in acid-base complexes have been surveyed. PMID:25353178

Solvent, Temperature And Concentration Effects on the Optical Activity of Chiral FIVE-And-SIX Membered Ring Ketones Conformers

NASA Astrophysics Data System (ADS)

Al-Basheer, Watheq

2017-06-01

Chiral five-and-six membered ring ketones are important molecules that are found in many biological systems and can exist in many possible conformers. In this talk, experimental and computational investigation of solvent, temperature and concentration effects on the circular dichroism (CD) and optical rotation (OR) of (R)-3 -methylcyclohexanone (R3MCH), (R)-3-methylcyclopentanone (R3MCP) and carvone conformers will be discussed. CD and OR measurements of these ketones gaseous samples and in ten common solvents of wide polarity range for different concentrations and sample temperatures were recorded and related to molecular conformation. Density functional theoretical calculations were performed using Gaussian09 at B3LYP functions with aug-cc-pVDZ level of theory. Also, CD and OR spectra for the optimized geometries of the ketones dominant conformers were computed over the ultraviolet and visible region in the gas phase as well as in ten solvents of varying polarity range, and under the umbrella of the polarizable continuum model (PCM). By comparing theoretical and experimental results, few thermodynamic parameters were deduced for the individual equatorial and axial conformers of each molecule in gas phase and in solvation.

A new high-speed hollow fiber based liquid phase microextraction method using volatile organic solvent for determination of aromatic amines in environmental water samples prior to high-performance liquid chromatography.

PubMed

Sarafraz-Yazdi, A; Mofazzeli, F; Es'haghi, Z

2009-07-15

A new and fast hollow fiber based liquid phase microextraction (HF-LPME) method using volatile organic solvents coupled with high-performance liquid chromatography (HPLC) was developed for determination of aromatic amines in the environmental water samples. Analytes including 3-nitroaniline, 3-chloroaniline and 4-bromoaniline were extracted from 6 mL basic aqueous sample solution (donor phase, NaOH 1 mol L(-1)) into the thin film of organic solvent that surrounded and impregnated the pores of the polypropylene hollow fiber wall (toluene, 20 microL), then back-extracted into the 6 mL acidified aqueous solution (acceptor phase, HCl 0.5 mol L(-1)) in the lumen of the two-end sealed hollow fiber. After the extraction, 5 microL of the acceptor phase was withdrawn into the syringe and injected directly into the HPLC system for the analysis. The parameters influencing the extraction efficiency including the kind of organic solvent and its volume, composition of donor and acceptor phases and the volume ratio between them, extraction time, stirring rate, salt addition and the effect of the analyte complexation with 18-crown-6 ether were investigated and optimized. Under the optimal conditions (donor phase: 6 mL of 1 mol L(-1) NaOH with 10% NaCl; organic phase: 20 microL of toluene; acceptor phase: 6 microL of 0.5 mol L(-1) HCl and 600 mmol L(-1) 18-crown-6 ether; pre-extraction and back-extraction times: 75 s and 10 min, respectively; stirring rate: 800 rpm), the obtained EFs were between 259 and 674, dynamic linear ranges were 0.1-1000 microg L(-1) (R>0.9991), and also the limits of detection were in the range of 0.01-0.1 micro gL(-1). The proposed procedure worked very well for real environmental water samples with microgram per liter level of the analytes, and good relative recoveries (91-102%) were obtained for the spiked sample solutions.

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

Nonadiabatic Photodynamics of a Retinal Model in Polar and Nonpolar Environment

PubMed Central

2013-01-01

The nonadiabatic photodynamics of the all-trans-2,4-pentadiene-iminium cation (protonated Schiff base 3, PSB3) and the all-trans-3-methyl-2,4-pentadiene-iminium cation (MePSB3) were investigated in the gas phase and in polar (aqueous) and nonpolar (n-hexane) solutions by means of surface hopping using a multireference configuration-interaction (MRCI) quantum mechanical/molecular mechanics (QM/MM) level. Spectra, lifetimes for radiationless deactivation to the ground state, and structural and electronic parameters are compared. A strong influence of the polar solvent on the location of the crossing seam, in particular in the bond length alternation (BLA) coordinate, is found. Additionally, inclusion of the polar solvent changes the orientation of the intersection cone from sloped in the gas phase to peaked, thus enhancing considerably its efficiency for deactivation of the molecular system to the ground state. These factors cause, especially for MePSB3, a substantial decrease in the lifetime of the excited state despite the steric inhibition by the solvent. PMID:23470211

Supercritical crystallization: The RESs-process and the GAS-process

NASA Astrophysics Data System (ADS)

Berends, Edwin M.

1994-09-01

This Doctoral Ph.D. thesis describes the development of two novel crystallization processes utilizing supercritical fluids either as a solvent, the RESS-process, or as an anti-solvent, the GAS-process. In th RESS-process precipitation of the solute is performed by expansion of the solution over a nozzle to produce ultra-fine, monodisperse particles without any solvent inclusions. In the GAS-process a high pressure gas is dissolved into the liquid phase solvent, where it causes a volumetric expansion of this liquid solvent and lowers the equilibrium solubility. Particle size, particle size distribution and other particle characteristics such as their shape, internal structure and the residual amount of solvent in the particles are expected to be influenced by the liquid phase expansion profile.

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

Cooperative CO2 Absorption Isotherms from a Bifunctional Guanidine and Bifunctional Alcohol.

PubMed

Steinhardt, Rachel; Hiew, Stanley C; Mohapatra, Hemakesh; Nguyen, Du; Oh, Zachary; Truong, Richard; Esser-Kahn, Aaron

2017-12-27

Designing new liquids for CO 2 absorption is a challenge in CO 2 removal. Here, achieving low regeneration energies while keeping high selectivity and large capacity are current challenges. Recent cooperative metal-organic frameworks have shown the potential to address many of these challenges. However, many absorbent systems and designs rely on liquid capture agents. We present herein a liquid absorption system which exhibits cooperative CO 2 absorption isotherms. Upon introduction, CO 2 uptake is initially suppressed, followed by an abrupt increase in absorption. The liquid consists of a bifunctional guanidine and bifunctional alcohol, which, when dissolved in bis(2-methoxyethyl) ether, forms a secondary viscous phase within seconds in response to increases in CO 2 . The precipitation of this second viscous phase drives CO 2 absorption from the gas phase. The isotherm of the bifunctional system differs starkly from the analogous monofunctional system, which exhibits limited CO 2 uptake across the same pressure range. In our system, CO 2 absorption is strongly solvent dependent. In DMSO, both systems exhibit hyperbolic isotherms and no precipitation occurs. Subsequent 1 H NMR experiments confirmed the formation of distinct alkylcarbonate species having either one or two molecules of CO 2 bound. The solvent and structure relationships derived from these results can be used to tailor new liquid absorption systems to the conditions of a given CO 2 separation process.

Neutron scattering as a probe of liquid crystal polymer-reinforced composite materials

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

Hjelm, R.P.; Douglas, E.P.; Benicewicz, B.C.

1995-12-31

This is the final report of a three-year Laboratory-Directed Research and Development (LDRD) project at the Los Alamos National Laboratory (LANL). This research project sought to obtain nanoscale and molecular level information on the mechanism of reinforcement in liquid crystal polymer (LCP)-reinforced composites, to realize molecular-reinforced LCP composites, and to test the validity of the concept of molecular reinforcement. Small-angle neutron scattering was used to study the structures in the ternary phase diagram of LCP with liquid crystal thermosets and solvent on length scales ranging from 1-100 nm. The goal of the scattering measurements is to understand the phase morphologymore » and degree of segregation of the reinforcing and matrix components. This information helps elucidate the physics of self assembly in these systems. This work provides an experimental basis for a microengineering approach to composites of vastly improved properties.« less

Experimental and theoretical study on DPPH radical scavenging mechanism of some chalcone quinoline derivatives

NASA Astrophysics Data System (ADS)

Hamlaoui, Ikram; Bencheraiet, Reguia; Bensegueni, Rafik; Bencharif, Mustapha

2018-03-01

In this study, the antioxidant capacity of three chalcone derivatives was evaluated by DPPH free radical scavenging. Experimental data showed low antioxidant activity (IC50±SD) of these molecules in comparison with BHT. The mechanism of DPPH radical scavenging elucidated by means of density functional theory (DFT) calculations. The tested compounds and their corresponding radicals and anions were optimized using B3LYP functional with 6-31G (d,p) basis set in the gas phase. The C-PCM model was used to perform solvent medium calculations. On the basis of theoretical calculations, it was shown that HAT mechanism was predominant in the gas phase, whereas SET-PT and SPLET mechanisms were favored in the presence of the solvent. Moreover, the HOMO orbitals and spin density distribution was evaluated to predict the probable sites for free radical attack.

A Density Functional Theory Evaluation of Hydrophobic Solvation: Ne, Ar and Kr in a 50-Water Cluster. Implications for the Hydrophobic Effect.

PubMed

Kobko, Nadya; Marianski, Mateusz; Asensio, Amparo; Wieczorek, Robert; Dannenberg, J J

2012-06-15

The physical explanation for the hydrophobic effect has been the subject of disagreement. Physical organic chemists tend to use a explanation related to pressure, while many biochemists prefer an explanation that involves decreased entropy of the aqueous solvent. We present DFT calculations at the B3LYP/6-31G(d,p) and X3LYP/6-31G(d,p) levels on the solvation of three noble gases (Ne, Ar, and Kr) in clusters of 50 waters. Vibrational analyses show no substantial decreases in the vibrational entropies of the waters in any of the three clusters. The observed positive free energies of transfer from the gas phase or from nonpolar solvents to water appear to be due to the work needed to make a suitable hole in the aqueous solvent. We distinguish between hydrophobic solvations (explicitly studied here) and the hydrophobic effect that occurs when a solute (or transition state) can decrease its volume through conformational change (which is not possible for the noble gases).

A Density Functional Theory Evaluation of Hydrophobic Solvation: Ne, Ar and Kr in a 50-Water Cluster. Implications for the Hydrophobic Effect

PubMed Central

Kobko, Nadya; Marianski, Mateusz; Asensio, Amparo; Wieczorek, Robert; Dannenberg, J. J.

2011-01-01

The physical explanation for the hydrophobic effect has been the subject of disagreement. Physical organic chemists tend to use a explanation related to pressure, while many biochemists prefer an explanation that involves decreased entropy of the aqueous solvent. We present DFT calculations at the B3LYP/6-31G(d,p) and X3LYP/6-31G(d,p) levels on the solvation of three noble gases (Ne, Ar, and Kr) in clusters of 50 waters. Vibrational analyses show no substantial decreases in the vibrational entropies of the waters in any of the three clusters. The observed positive free energies of transfer from the gas phase or from nonpolar solvents to water appear to be due to the work needed to make a suitable hole in the aqueous solvent. We distinguish between hydrophobic solvations (explicitly studied here) and the hydrophobic effect that occurs when a solute (or transition state) can decrease its volume through conformational change (which is not possible for the noble gases). PMID:22666658

Theoretical tuning of the firefly bioluminescence spectra by the modification of oxyluciferin

NASA Astrophysics Data System (ADS)

Cheng, Yuan-Yuan; Zhu, Jia; Liu, Ya-Jun

2014-01-01

Extending the firefly bioluminescence is of practical significance for the improved visualization of living cells and the development of a multicolor reporter. Tuning the color of bioluminescence in fireflies mainly involves the modification of luciferase and luciferin. In this Letter, we theoretically studied the emission spectra of 9 firefly oxyluciferin analogs in the gas phase and in solutions. Three density functionals, including B3LYP, CAM-B3LYP and M06-2X, were employed to theoretically predict the efficiently luminescent analogs. The reliable functionals for calculating the targeted systems were suggested. The luminescence efficiency, solvent effects, and substituent effects are discussed based on the calculated results.

Protein instability toward organic solvent/water emulsification: implications for protein microencapsulation into microspheres.

PubMed

Sah, H

1999-01-01

The objective of this study was to investigate the behavior of three proteins at an organic solvent/water interface. To simulate the first microencapsulation step of a water-in-oil-in-water emulsion technique, a water-in-oil emulsion was prepared by emulsifying an aqueous protein solution in either methylene chloride or ethyl acetate. Phase separation was then followed to collect protein samples from the aqueous phase and the organic solvent/water interface. Their properties were assessed by sodium dodecyl sulfate-polyacrylamide gel electrophoresis and size exclusion-HPLC. Bovine serum albumin was relatively unharmed during emulsification, compared to other proteins such as ovalbumin and lysozyme. In particular, the methylene chloride treatment on ovalbumin led to the formation of a large quantity of water-insoluble, solid-like aggregates and changes in the composition of monomeric and dimeric ovalbumin species. With regard to the question of ovalbumin recovery, only 9.74 approximately 37.72% of the used ovalbumin was present in the aqueous phases after emulsification. Similar penchant was noted with lysozyme. Water-insoluble aggregates brought with by emulsification were found to be covalently bound. Interestingly, less emulsification-induced denaturing effects were observed with ethyl acetate. Our study clearly demonstrated the emulsification-induced adverse events that were detrimental to the integrity of proteins and the importance of preserving protein stability toward microencapsulation.

Process for removing polychlorinated biphenyls from soil

DOEpatents

Hancher, C.W.; Saunders, M.B.; Googin, J.M.

1984-11-16

The present invention relates to a method of removing polychlorinated biphenyls from soil. The polychlorinated biphenyls are extracted from the soil by employing a liquid organic solvent dispersed in water in the ratio of about 1:3 to 3:1. The organic solvent includes such materials as short-chain hydrocarbons including kerosene or gasoline which are immiscible with water and are nonpolar. The organic solvent has a greater affinity for the PCB's than the soil so as to extract the PCB's from the soil upon contact. The organic solvent phase is separated from the suspended soil and water phase and distilled for permitting the recycle of the organic solvent phase and the concentration of the PCB's in the remaining organic phase. The present process can be satisfactorily practiced with soil containing 10 to 20% petroleum-based oils and organic fluids such as used in transformers and cutting fluids, coolants and the like which contain PCB's. The subject method provides for the removal of a sufficient concentration of PCB's from the soil to provide the soil with a level of PCB's within the guidelines of the Environmental Protection Agency.

Solvent effects and polymorphic transformation of organic nonlinear optical crystal L-pyroglutamic acid in solution growth processes . I. Solvent effects and growth morphology

NASA Astrophysics Data System (ADS)

Wang, W. S.; Aggarwal, M. D.; Choi, J.; Gebre, T.; Shields, Angela D.; Penn, Benjamin G.; Frazier, Donald O.

1999-03-01

Single crystals of a new promising nonlinear optical material for the tunable UV harmonic generation, L-pyroglutamic acid 60×20×20 mm 3 in size were obtained from aqueous solution by using the temperature-lowering method. Solubility of L-pyroglutamic acid in different solvents was measured. The single crystals showed different morphological characteristics and growth rate in different solvents with different crystallographic orientations. Methanol or ethanol solutions yielded needle-like crystals. In mixed solution such as methanol/H 2O or ethanol/ H 2O plate-like crystals with a thickness in the direction [0 1 0] were observed. The water as a good solvent, however, produced long prism-like crystals. The two polymorphs of L-pyroglutamic acid (α and β phases) were found for the first time. The growth shapes of α-phase is mainly a prism and β phases is a rhombic plate.The growth rate of α and β phases is mainly a function of the supersaturation of the L-pyroglutamic acid in solution.

Molecular dynamics study of polysaccharides in binary solvent mixtures of an ionic liquid and water.

PubMed

Liu, Hanbin; Sale, Kenneth L; Simmons, Blake A; Singh, Seema

2011-09-01

Some ionic liquids (ILs) have great promise as effective solvents for biomass pretreatment, and there are several that have been reported that can dissolve large amounts of cellulose. The solubilized cellulose can then be recovered by addition of antisolvents, such as water or ethanol, and this regeneration process plays an important role in the subsequent enzymatic saccharification reactions and in the recovery of the ionic liquid. To date, little is known about the fundamental intermolecular interactions that drive the dissolution and subsequent regeneration of cellulose in complex mixtures of ionic liquids, water, and cellulose. To investigate these interactions, in this work, molecular dynamics (MD) simulations were carried out to study binary and ternary mixtures of the ionic liquid 1-ethyl-3-methylimidazolium acetate ([C2mim][OAc]) with water and a cellulose oligomer. Simulations of a cellulose oligomer dissolved in three concentrations of binary mixtures of [C2mim][OAc] and water were used to represent the ternary system in the dissolution phase (high [C2mim][OAc] concentration) and present during the initial phase of the regeneration step (intermediate and low [C2mim][OAc] concentrations). The MD analysis of the structure and dynamics that exist in these binary and ternary mixtures provides information on the key intermolecular interactions between cellulose and [C2mim][OAc] that lead to dissolution of cellulose and the key intermolecular interactions in the intermediate states of cellulose precipitation as a function of water content in the cellulose/IL/water system. The analysis of this intermediate state provides new insight into the molecular driving forces present in this ternary system. © 2011 American Chemical Society

Preparation and physicochemical characteristics of polylactide microspheres of emamectin benzoate by modified solvent evaporation/extraction method.

PubMed

Zhang, Shao Fei; Chen, Peng Hao; Zhang, Fei; Yang, Yan Fang; Liu, De Kun; Wu, Gang

2013-12-18

Emamectin benzoate is highly effective against insect pests and widely used in the world. However, its biological activity is limited because of high resistance of target insects and rapid degradation speed in fields. Preparation and physicochemical characterization of degradable microcapsules of emamectin benzoate were studied by modified solvent evaporation/extraction method using polylactide (PLA) as wall material. The influence of different compositions of the solvent in internal organic phase and external aqueous phase on diameter, span, pesticide loading, and entrapment rate of the microspheres was investigated. The results indicated that the process of solvent extraction and the formation of the microcapsules would be accelerated by adding water-miscible organic solvents such as ethyl ether, acetone, ethyl acetate, or n-butanol into internal organic phase and external aqueous phase. Accelerated formation of the microcapsules would result in entrapment rates of emamectin benzoate increased to as high as 97%. In addition, by adding ethanol into the external aqueous phase, diameters would reduce to 6.28 μm, whereas the loading efficiency of emamectin benzoate did not increase. The PLA microspheres prepared under optimum conditions were smoother and more spherical. The degradation rate in PLA microspheres of emamectin benzoate on the 10th day was 4.29 ± 0.74%, whereas the degradation rates of emamectin benzoate in methanol solution and solid technical material were 46.3 ± 2.11 and 22.7 ± 1.51%, respectively. The PLA skeleton had combined with emamectin benzoate in an amorphous or molecular state by using differential scanning calorimetry (DSC) determination. The results indicated that PLA microspheres of emamectin benzoate with high entrapment rate, loading efficiency, and physicochemical characteristics could be obtained by adding water-miscible organic solvents into the internal organic phase and external aqueous phase.

Catalytic asymmetric dihydroxylation of olefins using a recoverable and reusable OsO(4)2- in ionic liquid [bmim][PF6].

PubMed

Branco, Luís C; Afonso, Carlos A M

2002-12-21

The use of the solvent systems water/ionic liquid or water/ionic liquid/tert-butanol provides a recoverable, reusable, robust and simple system for the asymmetric dihydroxylation of olefins, based on the immobilization of the osmium-ligand catalyst in the ionic liquid phase.

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.

Role of solvent-mediated carbodiimide cross-linking in fabrication of electrospun gelatin nanofibrous membranes as ophthalmic biomaterials.

PubMed

Chou, Shih-Feng; Luo, Li-Jyuan; Lai, Jui-Yang; Ma, David Hui-Kang

2017-02-01

Due to their ability to mimic the structure of extracellular matrix, electrospun gelatin nanofibers are promising cell scaffolding materials for tissue engineering applications. However, the hydrophilic gelatin molecules usually need stabilization before use in aqueous physiological environment. Considering that biomaterials cross-linked via film immersion technique may have a more homogeneous cross-linked structure than vapor phase cross-linking, this work aims to investigate the chemical modification of electrospun gelatin nanofibrous membranes by liquid phase carbodiimide in the presence of ethanol/water co-solvents with varying ethanol concentrations ranging from 80 to 99.5vol%. The results of characterization showed that increasing water content in the binary reaction solvent system increases the extent of cross-linking of gelatin nanofibers, but simultaneously promotes the effect of biopolymer swelling and distortion in fiber mat structure. As compared to non-cross-linked counterparts, carbodiimide treated gelatin nanofibrous mats exhibited better thermal and biological stability where the shrinkage temperature and resistance to enzymatic degradation varied in response to ethanol/water solvent composition-mediated generation of cross-links. Irrespective of their cross-linking density, all studied membrane samples did not induce any responses in ocular epithelial cell cultures derived from cornea, lens, and retina. Unlike many other cross-linking agents and/or methods (e.g., excessive vapor phase cross-linking) that may pose a risk of toxicity, our study demonstrated that these nanofibrous materials are well tolerated by anterior segment tissues. These findings also indicate the safety of using ethanol/water co-solvents for chemical cross-linking of gelatin to engineer nanofibrous materials with negligible biological effects. In summary, the present results suggest the importance of solvent-mediated carbodiimide cross-linking in modulating structure-property relationship without compromising in vitro and in vivo biocompatibility of electrospun gelatin nanofibers for future ophthalmic applications. Copyright © 2016 Elsevier B.V. All rights reserved.

A novel and organic solvent-free preparation of solid lipid nanoparticles using natural biopolymers as emulsifier and stabilizer.

PubMed

Xue, Jingyi; Wang, Taoran; Hu, Qiaobin; Zhou, Mingyong; Luo, Yangchao

2017-10-05

In this work, a new and novel organic solvent-free and synthetic surfactant-free method was reported to fabricate stable solid lipid nanoparticles (SLNs) from stearic acid, sodium caseinate (NaCas) and pectin, as well as water. Melted stearic acid was directly emulsified into an aqueous phase containing NaCas and pectin, followed by pH adjustment and thermal treatment to induce the formation of a compact and dense polymeric coating which stabilized SLNs. The preparation procedures and formulations were comprehensively optimized. The inter- and intra-molecular interactions among three ingredients were characterized by fluorescence and Fourier transform infrared spectroscopies. The stability of as-prepared SLNs was evaluated under simulated gastrointestinal conditions, and compared with traditional SLNs prepared with organic solvents. Our results revealed that the SLNs prepared from this organic solvent-free method had superior physicochemical properties over the traditional SLNs, including smaller size and better stability. Furthermore, redispersible SLNs powders were obtained by nano spray drying, but only the SLNs prepared by organic solvent-free method had sub-micron scale, uniform and spherical morphology. The organic solvent-free preparation method was proved to be a promising approach to prepare stable and uniform SLNs for potential oral delivery applications. Copyright © 2017 Elsevier B.V. All rights reserved.

Solvation effects on chemical shifts by embedded cluster integral equation theory.

PubMed

Frach, Roland; Kast, Stefan M

2014-12-11

The accurate computational prediction of nuclear magnetic resonance (NMR) parameters like chemical shifts represents a challenge if the species studied is immersed in strongly polarizing environments such as water. Common approaches to treating a solvent in the form of, e.g., the polarizable continuum model (PCM) ignore strong directional interactions such as H-bonds to the solvent which can have substantial impact on magnetic shieldings. We here present a computational methodology that accounts for atomic-level solvent effects on NMR parameters by extending the embedded cluster reference interaction site model (EC-RISM) integral equation theory to the prediction of chemical shifts of N-methylacetamide (NMA) in aqueous solution. We examine the influence of various so-called closure approximations of the underlying three-dimensional RISM theory as well as the impact of basis set size and different treatment of electrostatic solute-solvent interactions. We find considerable and systematic improvement over reference PCM and gas phase calculations. A smaller basis set in combination with a simple point charge model already yields good performance which can be further improved by employing exact electrostatic quantum-mechanical solute-solvent interaction energies. A larger basis set benefits more significantly from exact over point charge electrostatics, which can be related to differences of the solvent's charge distribution.

Face-Dependent Solvent Adsorption: A Comparative Study on the Interfaces of HMX Crystal with Three Solvents.

PubMed

Liu, Yingzhe; Lai, Weipeng; Ma, Yiding; Yu, Tao; Kang, Ying; Ge, Zhongxue

2017-07-27

To understand the crystal-solvent interfacial interactions on the molecular scale, the interfaces between three solvents, that is, acetone, γ-butyrolactone, and cyclohexanone, and three growth faces of 1,3,5,7-tetranitro-1,3,5,7-tetrazocane (HMX) crystal have been investigated with the aid of theoretical chemistry. The results show that the structural features of crystal faces play a critical role in the energetic, structural, and dynamic properties at the interfaces. For each solvent, the same change trend of some properties among the three faces of HMX crystal is observed, including adsorption affinity, local mass density, and solvent diffusion. For example, the rate of solvent diffusion at the three faces ranks as (011) > (110) > (020) regardless of solvent species. This can be attributed to the similar adsorption sites for solvent incorporation at the same face, which are concentrated at the cavities formed by surficial HMX molecules.

The development of a high-throughput measurement method of octanol/water distribution coefficient based on hollow fiber membrane solvent microextraction technique.

PubMed

Bao, James J; Liu, Xiaojing; Zhang, Yong; Li, Youxin

2014-09-15

This paper describes the development of a novel high-throughput hollow fiber membrane solvent microextraction technique for the simultaneous measurement of the octanol/water distribution coefficient (logD) for organic compounds such as drugs. The method is based on a designed system, which consists of a 96-well plate modified with 96 hollow fiber membrane tubes and a matching lid with 96 center holes and 96 side holes distributing in 96 grids. Each center hole was glued with a sealed on one end hollow fiber membrane tube, which is used to separate the aqueous phase from the octanol phase. A needle, such as microsyringe or automatic sampler, can be directly inserted into the membrane tube to deposit octanol as the accepted phase or take out the mixture of the octanol and the drug. Each side hole is filled with aqueous phase and could freely take in/out solvent as the donor phase from the outside of the hollow fiber membranes. The logD can be calculated by measuring the drug concentration in each phase after extraction equilibrium. After a comprehensive comparison, the polytetrafluoroethylene hollow fiber with the thickness of 210 μm, an extraction time of 300 min, a temperature of 25 °C and atmospheric pressure without stirring are selected for the high throughput measurement. The correlation coefficient of the linear fit of the logD values of five drugs determined by our system to reference values is 0.9954, showed a nice accurate. The -8.9% intra-day and -4.4% inter-day precision of logD for metronidazole indicates a good precision. In addition, the logD values of eight drugs were simultaneously and successfully measured, which indicated that the 96 throughput measure method of logD value was accurate, precise, reliable and useful for high throughput screening. Copyright © 2014 Elsevier B.V. All rights reserved.

A review: fabrication of porous polyurethane scaffolds.

PubMed

Janik, H; Marzec, M

2015-03-01

The aim of tissue engineering is the fabrication of three-dimensional scaffolds that can be used for the reconstruction and regeneration of damaged or deformed tissues and organs. A wide variety of techniques have been developed to create either fibrous or porous scaffolds from polymers, metals, composite materials and ceramics. However, the most promising materials are biodegradable polymers due to their comprehensive mechanical properties, ability to control the rate of degradation and similarities to natural tissue structures. Polyurethanes (PUs) are attractive candidates for scaffold fabrication, since they are biocompatible, and have excellent mechanical properties and mechanical flexibility. PU can be applied to various methods of porous scaffold fabrication, among which are solvent casting/particulate leaching, thermally induced phase separation, gas foaming, emulsion freeze-drying and melt moulding. Scaffold properties obtained by these techniques, including pore size, interconnectivity and total porosity, all depend on the thermal processing parameters, and the porogen agent and solvents used. In this review, various polyurethane systems for scaffolds are discussed, as well as methods of fabrication, including the latest developments, and their advantages and disadvantages. Copyright © 2014. Published by Elsevier B.V.

Dry coating of solid dosage forms: an overview of processes and applications.

PubMed

Foppoli, Anastasia Anna; Maroni, Alessandra; Cerea, Matteo; Zema, Lucia; Gazzaniga, Andrea

2017-12-01

Dry coating techniques enable manufacturing of coated solid dosage forms with no, or very limited, use of solvents. As a result, major drawbacks associated with both organic solvents and aqueous coating systems can be overcome, such as toxicological, environmental, and safety-related issues on the one hand as well as costly drying phases and impaired product stability on the other. The considerable advantages related to solventless coating has been prompting a strong research interest in this field of pharmaceutics. In the article, processes and applications relevant to techniques intended for dry coating are analyzed and reviewed. Based on the physical state of the coat-forming agents, liquid- and solid-based techniques are distinguished. The former include hot-melt coating and coating by photocuring, while the latter encompass press coating and powder coating. Moreover, solventless techniques, such as injection molding and three-dimensional printing by fused deposition modeling, which are not purposely conceived for coating, are also discussed in that they would open new perspectives in the manufacturing of coated-like dosage forms.

Comparative density functional study of the complexes [UO2(CO3)3]4- and [(UO2)3(CO3)6]6- in aqueous solution.

PubMed

Schlosser, Florian; Moskaleva, Lyudmila V; Kremleva, Alena; Krüger, Sven; Rösch, Notker

2010-06-28

With a relativistic all-electron density functional method, we studied two anionic uranium(VI) carbonate complexes that are important for uranium speciation and transport in aqueous medium, the mononuclear tris(carbonato) complex [UO(2)(CO(3))(3)](4-) and the trinuclear hexa(carbonato) complex [(UO(2))(3)(CO(3))(6)](6-). Focusing on the structures in solution, we applied for the first time a full solvation treatment to these complexes. We approximated short-range effects by explicit aqua ligands and described long-range electrostatic interactions via a polarizable continuum model. Structures and vibrational frequencies of "gas-phase" models with explicit aqua ligands agree best with experiment. This is accidental because the continuum model of the solvent to some extent overestimates the electrostatic interactions of these highly anionic systems with the bulk solvent. The calculated free energy change when three mono-nuclear complexes associate to the trinuclear complex, agrees well with experiment and supports the formation of the latter species upon acidification of a uranyl carbonate solution.

Microporous polymer films and methods of their production

DOEpatents

Aubert, James H.

1995-01-01

A process for producing thin microporous polymeric films for a variety of uses. The process utilizes a dense gas (liquified gas or supercritical fluid) selected to combine with a solvent-containing polymeric film so that the solvent is dissolved in the dense gas, the polymer is substantially insoluble in the dense gas, and two phases are formed. A microporous film is obtained by removal of a dense gas-solvent phase.

Dispersions of Goethite Nanorods in Aprotic Polar Solvents

PubMed Central

Coursault, Delphine; Dozov, Ivan; Nobili, Maurizio; Dupont, Laurent; Chanéac, Corinne

2017-01-01

Colloidal suspensions of anisotropic nanoparticles can spontaneously self-organize in liquid-crystalline phases beyond some concentration threshold. These phases often respond to electric and magnetic fields. At lower concentrations, usual isotropic liquids are observed but they can display very strong Kerr and Cotton-Mouton effects (i.e., field-induced particle orientation). For many examples of these colloidal suspensions, the solvent is water, which hinders most electro-optic applications. Here, for goethite (α-FeOOH) nanorod dispersions, we show that water can be replaced by polar aprotic solvents, such as N-methyl-2-pyrrolidone (NMP) and dimethylsulfoxide (DMSO), without loss of colloidal stability. By polarized-light microscopy, small-angle X-ray scattering and electro-optic measurements, we found that the nematic phase, with its field-response properties, is retained. Moreover, a strong Kerr effect was also observed with isotropic goethite suspensions in these polar aprotic solvents. Furthermore, we found no significant difference in the behavior of both the nematic and isotropic phases between the aqueous and non-aqueous dispersions. Our work shows that goethite nanorod suspensions in polar aprotic solvents, suitable for electro-optic applications, can easily be produced and that they keep all their outstanding properties. It also suggests that this solvent replacement method could be extended to the aqueous colloidal suspensions of other kinds of charged anisotropic nanoparticles. PMID:29039797

The solvent component of macromolecular crystals

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

Weichenberger, Christian X.; Afonine, Pavel V.; Kantardjieff, Katherine

2015-04-30

On average, the mother liquor or solvent and its constituents occupy about 50% of a macromolecular crystal. Ordered as well as disordered solvent components need to be accurately accounted for in modelling and refinement, often with considerable complexity. The mother liquor from which a biomolecular crystal is grown will contain water, buffer molecules, native ligands and cofactors, crystallization precipitants and additives, various metal ions, and often small-molecule ligands or inhibitors. On average, about half the volume of a biomolecular crystal consists of this mother liquor, whose components form the disordered bulk solvent. Its scattering contributions can be exploited in initialmore » phasing and must be included in crystal structure refinement as a bulk-solvent model. Concomitantly, distinct electron density originating from ordered solvent components must be correctly identified and represented as part of the atomic crystal structure model. Herein, are reviewed (i) probabilistic bulk-solvent content estimates, (ii) the use of bulk-solvent density modification in phase improvement, (iii) bulk-solvent models and refinement of bulk-solvent contributions and (iv) modelling and validation of ordered solvent constituents. A brief summary is provided of current tools for bulk-solvent analysis and refinement, as well as of modelling, refinement and analysis of ordered solvent components, including small-molecule ligands.« less

Fractionation of technical octabromodiphenyl ether by countercurrent chromatography combined with gas chromatography/mass spectrometry and offline and online (1)H nuclear magnetic resonance spectroscopy.

PubMed

Hammann, Simon; Conrad, Jürgen; Vetter, Walter

2015-06-12

Countercurrent chromatography (CCC) is a technique, which uses two immiscible liquid phases for a separation process in a long and hollow tube. The technique allows the separation of high amounts of sample (50mg to several grams) with a low consumption of solvents. In this study, we fractionated 50mg technical octabromodiphenyl ether (DE-79) and analyzed the fractions by gas chromatography with mass spectrometry (GC/MS) and proton nuclear magnetic resonance ((1)H NMR) spectroscopy. CCC separations were performed with n-hexane/acetonitrile as solvent system in tail-to-head (i.e. the upper phase is mobile) mode. Twelve CCC fractions were studied for the PBDE composition. CCC elution of PBDE congeners was dependent both on the degree of bromination and substitution pattern. Higher brominated congeners eluted faster than lower brominated congeners and isomers with vicinal hydrogen atoms eluted last. In addition to several known PBDE congeners in DE-79, we were able to unequivocally identify BDE 195 in DE-79 and we could verify the presence of BDE 184. Finally, we also established the online hyphenation of CCC with (1)H NMR. The use of deuterated solvents could be avoided by using n-hexane/acetonitrile as two-phase system. By online CCC-(1)H NMR in stop-flow mode we were able to detect eight PBDE congeners in the mixture. Copyright © 2015 Elsevier B.V. All rights reserved.

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

PubMed

Farajzadeh, Mir Ali; Khoshmaram, Leila

2015-01-30

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

Separation of switchgrass bio-oil by water/organic solvent addition and pH adjustment

DOE PAGES

Park, Lydia Kyoung-Eun; Ren, Shoujie; Yiacoumi, Sotira; ...

2016-01-29

Applications of bio-oil are limited by its challenging properties including high moisture content, low pH, high viscosity, high oxygen content, and low heating value. Separation of switchgrass bio-oil components by adding water, organic solvents (hexadecane and octane), and sodium hydroxide may help to overcome these issues. Acetic acid and phenolic compounds were extracted in aqueous and organic phases, respectively. Polar chemicals, such as acetic acid, did not partition in the organic solvent phase. Acetic acid in the aqueous phase after extraction is beneficial for a microbial-electrolysis-cell application to produce hydrogen as an energy source for further hydrodeoxygenation of bio-oil. Organicmore » solvents extracted more chemicals from bio-oil in combined than in sequential extraction; however, organic solvents partitioned into the aqueous phase in combined extraction. When sodium hydroxide was added to adjust the pH of aqueous bio-oil, organic-phase precipitation occurred. As the pH was increased, a biphasic aqueous/organic dispersion was formed, and phase separation was optimized at approximately pH 6. The neutralized organic bio-oil had approximately 37% less oxygen and 100% increased heating value than the initial centrifuged bio-oil. In conclusion, the less oxygen content and increased heating value indicated a significant improvement of the bio-oil quality through neutralization.« less

Separation of switchgrass bio-oil by water/organic solvent addition and pH adjustment

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

Park, Lydia Kyoung-Eun; Ren, Shoujie; Yiacoumi, Sotira

Applications of bio-oil are limited by its challenging properties including high moisture content, low pH, high viscosity, high oxygen content, and low heating value. Separation of switchgrass bio-oil components by adding water, organic solvents (hexadecane and octane), and sodium hydroxide may help to overcome these issues. Acetic acid and phenolic compounds were extracted in aqueous and organic phases, respectively. Polar chemicals, such as acetic acid, did not partition in the organic solvent phase. Acetic acid in the aqueous phase after extraction is beneficial for a microbial-electrolysis-cell application to produce hydrogen as an energy source for further hydrodeoxygenation of bio-oil. Organicmore » solvents extracted more chemicals from bio-oil in combined than in sequential extraction; however, organic solvents partitioned into the aqueous phase in combined extraction. When sodium hydroxide was added to adjust the pH of aqueous bio-oil, organic-phase precipitation occurred. As the pH was increased, a biphasic aqueous/organic dispersion was formed, and phase separation was optimized at approximately pH 6. The neutralized organic bio-oil had approximately 37% less oxygen and 100% increased heating value than the initial centrifuged bio-oil. In conclusion, the less oxygen content and increased heating value indicated a significant improvement of the bio-oil quality through neutralization.« less

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.

Understanding the Impact of Water on the Miscibility and Microstructure of Amorphous Solid Dispersions: An AFM-LCR and TEM-EDX Study.

PubMed

Li, Na; Gilpin, Christopher J; Taylor, Lynne S

2017-05-01

Miscibility is critical for amorphous solid dispersions (ASDs). Phase-separated ASDs are more prone to crystallization, and thus can lose their solubility advantage leading to product failure. Additionally, dissolution performance can be diminished as a result of phase separation in the ASD matrix. Water is known to induce phase separation during storage for some ASDs. However, the impact of water introduced during preparation has not been as thoroughly investigated to date. The purpose of this study was to develop a mechanistic understanding of the effect of water on the phase behavior and microstructure of ASDs. Evacetrapib and two polymers were selected as the model system. Atomic force microscopy coupled with Lorentz contact resonance, and transmission electron microscopy with energy dispersive X-ray spectroscopy were employed to evaluate the microstructure and composition of phase-separated ASDs. It was found that phase separation could be induced via two routes: solution-state phase separation during ASD formation caused by water absorption during film formation by a hydrophilic solvent, or solid-phase separation following exposure to high RH during storage. Water contents of as low as 2% in the organic solvent system used to dissolve the drug and polymer were found to result in phase separation in the resultant ASD film. These findings have profound implications on lab-scale ASD preparation and potentially also for industrial production. Additionally, these high-resolution imaging techniques combined with orthogonal analyses are powerful tools to visualize structural changes in ASDs, which in turn will enable better links to be made between ASD structure and performance.

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

PubMed

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

2017-03-08

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

Structure and Dynamics of Solvent Landscapes in Charge-Transfer Reactions

NASA Astrophysics Data System (ADS)

Leite, Vitor B. Pereira

The dynamics of solvent polarization plays a major role in the control of charge transfer reactions. The success of Marcus theory describing the solvent influence via a single collective quadratic polarization coordinate has been remarkable. Onuchic and Wolynes have recently proposed (J. Chem Phys 98 (3) 2218, 1993) a simple model demonstrating how a many-dimensional-complex model composed by several dipole moments (representing solvent molecules or polar groups in proteins) can be reduced under the appropriate limits into the Marcus Model. This work presents a dynamical study of the same model, which is characterized by two parameters, an average dipole-dipole interaction as a term associated with the potential energy landscape roughness. It is shown why the effective potential, obtained using a thermodynamic approach, is appropriate for the dynamics of the system. At high temperatures, the system exhibits effective diffusive one-dimensional dynamics, where the Born-Marcus limit is recovered. At low temperatures, a glassy phase appears with a slow non-self-averaging dynamics. At intermediate temperatures, the concept of equivalent diffusion paths and polarization dependence effects are discussed. This approach is extended to treat more realistic solvent models. Real solvents are discussed in terms of simple parameters described above, and an analysis of how different regimes affect the rate of charge transfer is presented. Finally, these ideas are correlated to analogous problems in other areas.

Terra-Kleen Response Group, Inc. Solvent Extraction Technology Rapid Commercialization Initiative Report

EPA Science Inventory

Terra-Kleen Response Group Inc. (Terra-Kleen), has commercialized a solvent extraction technology that uses a proprietary extraction solvent to transfer organic constituents from soil to a liquid phase in a batch process at ambient temperatures. The proprietary solvent has a rel...

Extraction of phenol in wastewater with annular centrifugal contactors.

PubMed

Xu, Jin-Quan; Duan, Wu-Hua; Zhou, Xiu-Zhu; Zhou, Jia-Zhen

2006-04-17

Solvent extraction is an effective way to treat and recover the phenolic compounds from the high content phenolic wastewater at present. The experimental study on treating the wastewater containing phenol has been carried out with QH-1extractant (the amine mixture) and annular centrifugal contactors. The distribution ratio of phenol was 108.6 for QH-1-phenol system. The mass-transfer process of phenol for the system was mainly controlled by diffusion. When the flow ratio (aqueous/organic) was changed from 1/1 to 4/1, the rotor speed was changed from 2500 to 4000 r/min, and the total flow of two phases was changed from 20 to 70 mL/min, the mass-transfer efficiency E of the single-stage centrifugal contactor was more than 95%. When the flow ratio was changed from 4.4/1 to 4.9/1, the rotor speed was 3000 r/min, and the total flow of two phases was changed from 43.0 to 47.0 mL/min, the extraction rate rho of the three-stage cascade was more than 99%. When 15% NaOH was used for stripping of phenol in QH-1, the stripping efficiency of the three-stage cascade was also more than 99% under the experimental conditions.

Preparative isolation and purification of astaxanthin from the microalga Chlorococcum sp. by high-speed counter-current chromatography.

PubMed

Li, H B; Chen, F

2001-08-03

High-speed counter-current chromatography was applied to the isolation and purification of astaxanthin from microalgae. The crude astaxanthin was obtained by extraction with organic solvents after the astaxanthin esters were saponified. Preparative high-speed counter-current chromatography with a two-phase solvent system composed of n-hexane-ethyl acetate-ethanol-water (5:5:6.5:3, v/v) was successfully performed yielding astaxanthin at 97% purity from 250 mg of the crude extract in a one-step separation.

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

Solvation effects on alanine dipeptide: A MP2/cc-pVTZ//MP2/6-31G** study of (Phi, Psi) energy maps and conformers in the gas phase, ether, and water.

PubMed

Wang, Zhi-Xiang; Duan, Yong

2004-11-15

The effects of solvation on the conformations and energies of alanine dipeptide (AD) have been studied by ab initio calculations up to MP2/cc-pVTZ//MP2/6-31G**, utilizing the polarizable continuum model (PCM) to mimic solvation effects. The energy surfaces in the gas phase, ether, and water bear similar topological features carved by the steric hindrance, but the details differ significantly due to the solvent effects. The gas-phase energy map is qualitatively consistent with the Ramachandran plot showing seven energy minima. With respect to the gas-phase map, the significant changes of the aqueous map include (1) the expanded low-energy regions, (2) the emergence of an energy barrier between C5-beta and alpha(R)-beta(2) regions, (3) a clearly pronounced alpha(R) minimum, a new beta-conformer, and the disappearance of the gas-phase global minimum, and (4) the shift of the dominant region in LEII from the gas-phase C7(ax) region to the alpha(L) region. These changes bring the map in water to be much closer to the Ramachandran plot than the gas-phase map. The solvent effects on the geometries include the elongation of the exposed N-H and C=O bonds, the shortening of the buried HN--CO peptide bonds, and the enhanced planarity of the peptide bonds. The energy surface in ether has features similar to those both in the gas phase and in water. The free energy order computed in the gas phase and in ether is in good agreement with experimental studies that concluded that C5 and C7(eq) are the dominant species in both the gas phase and nonpolar solvents. The free energy order in water is consistent with the experimental observation that the dominant C7(eq) in the nonpolar solvent was largely replaced by P(II)-like (i.e., beta) and alpha(R) in the strong polar solvents. Based on calculations on AD + 4H(2)O and other AD-water clusters, we suggest that explicit water-AD interactions may distort C5 and beta (or alpha(R) and beta) to an intermediate conformation. Our analysis also shows that the PCM calculations at the MP2/cc-pVTZ//MP2/6-31G** level give good descriptions to the bulk solvent polarization effect. The results presented in this article should be of sufficient quality to characterize the peptide bonds in the gas phase and solvents. The energy surfaces may serve as the basis for developing of strategies enabling the inclusion of solvent polarization in the force field.

Microporous polymer films and methods of their production

DOEpatents

Aubert, J.H.

1995-06-06

A process is described for producing thin microporous polymeric films for a variety of uses. The process utilizes a dense gas (liquefied gas or supercritical fluid) selected to combine with a solvent-containing polymeric film so that the solvent is dissolved in the dense gas, the polymer is substantially insoluble in the dense gas, and two phases are formed. A microporous film is obtained by removal of a dense gas-solvent phase. 9 figs.

Resveratrol cocrystals with enhanced solubility and tabletability.

PubMed

Zhou, Zhengzheng; Li, Wanying; Sun, Wei-Jhe; Lu, Tongbu; Tong, Henry H Y; Sun, Changquan Calvin; Zheng, Ying

2016-07-25

Two new 1:1 cocrystals of resveratrol (RES) with 4-aminobenzamide (RES-4ABZ) and isoniazid (RES-ISN) were synthesized by liquid assisted grinding (LAG) and rapid solvent removal (RSR) methods using ethanol as solvent. Their physiochemical properties were characterized using PXRD, DSC, solid state and solution NMR, FT-IR, and HPLC. Pharmaceutically relevant properties, including tabletability, solubility, intrinsic dissolution rate, and hygroscopicity, were evaluated. Temperature-composition phase diagram for RES-ISN cocrystal system was constructed from DSC data. Both cocrystals show higher solubility than resveratrol over a broad range of pH. They are phase stable and non-hygroscopic even under high humidity conditions. Importantly, both cocrystals exhibit improved solubility and tabletability compared with RES, which make them more suitable candidates for tablet formulation development. Copyright © 2016 Elsevier B.V. All rights reserved.

Asymmetric lipid-polymer particles (LIPOMER) by modified nanoprecipitation: role of non-solvent composition.

PubMed

Jindal, Anil B; Devarajan, Padma V

2015-07-15

Asymmetric lipid polymer nanostructures (LIPOMER) comprising glyceryl monostearate (GMS) as lipid and Gantrez AN 119 (Gantrez) as polymer, revealed enhanced splenic accumulation. In the present paper, we attempt to explain the formation of asymmetric GMS LIPOMER using real time imaging. Particles were prepared by precipitation under static conditions using different non-solvent phase compositions. The process was video recorded and the videos converted to time elapsed images using the FFmpeg 0.10.2 software at 25 frames/sec. Non-solvent compositions comprising >30% of IPA/Acetone revealed significant stranding of the solvent phase and slower onset of precipitation(2-6s). At lower concentrations of IPA and acetone, and in non-solvent compositions comprising ethanol/water the stranding phenomenon was not evident. Further, rapid precipitation(<1 s) was evident. Nanoprecipitation based on the Marangoni effect is a result of diffusion stranding, interfacial turbulence, and mass transfer of solvent and non-solvent resulting in solute precipitation. Enhanced diffusion stranding favored by high interaction of GMS and Gantrez(low ΔPol), and the low solubility parameter(Δδtotal) and high mixing enthalpy(ΔHM) of GMS in IPA resulted in droplets with random shapes analogous to an amoeba with pseudopodia, which on precipitation formed asymmetric particles. Asymmetric particles could be readily designed through appropriate selection of solutes and non-solvent phase by modified nanoprecipitation. Copyright © 2015 Elsevier B.V. All rights reserved.

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.

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.

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.

ESR imaging investigations of two-phase systems.

PubMed

Herrmann, Werner; Stösser, Reinhard; Borchert, Hans-Hubert

2007-06-01

The possibilities of electron spin resonance (ESR) and electron spin resonance imaging (ESRI) for investigating the properties of the spin probes TEMPO and TEMPOL in two-phase systems have been examined in the systems water/n-octanol, Miglyol/Miglyol, and Precirol/Miglyol. Phases and regions of the phase boundary could be mapped successfully by means of the isotropic hyperfine coupling constants, and, moreover, the quantification of rotational and lateral diffusion of the spin probes was possible. For the quantitative treatment of the micropolarity, a simplified empirical model was established on the basis of the Nernst distribution and the experimentally determined isotropic hyperfine coupling constants. The model does not only describe the summarized micropolarities of coexisting phases, but also the region of the phase boundary, where solvent molecules of different polarities and tendencies to form hydrogen bonds compete to interact with the NO group of the spin probe. Copyright 2007 John Wiley & Sons, Ltd.

Determination of Three Organochlorine Pesticides in Aqueous Samples by Solid-Phase Extraction Based on Natural Nano Diatomite in Packed Syringe Coupled to Gas Chromatography-Mass Spectrometry.

PubMed

Taghani, Abdollah; Goudarzi, Nasser; Bagherian, Ghadamali; Chamjangali, Mansour Arab

2017-01-01

A rapid, simple, and sensitive technique is proposed based on a miniaturized solid-phase extraction method named mictroextraction in a packed syringe coupled with gas chromatography-mass spectrometry for the preconcentration and determination of three organochlorine pesticides. These include hexachlorobenzene, heptachlor and aldrine in aqueous samples. For the first time, the natural nano diatomite is used a sorbent. Based on this technique, 6.0 mg of the nano sorbent is inserted in a syringe between two polypropylene frits. The analytes would be adsorbed on the solid phase, and would subsequently be eluted using organic solvents. The influence of some important parameters, such as the solution pH, type and volume of the organic desorption solvent, and amount of sorbent on the extraction efficiency of the selected pesticides, is investigated. The proposed method shows good linearity in the range of 0.1 - 40.0 μg L -1 , and at low limits of detection in the range of 0.02 - 0.13 μg L -1 using the selected ion-monitoring mode. The reproducibility of this method was found to be in the range of 3.5 - 11.1% for the understudied pesticides. In order to evaluate the matrix effect, the developed method is also applied to the preconcentration and determination of the selected pesticides in different water samples.

Sensitive determination of three aconitum alkaloids and their metabolites in human plasma by matrix solid-phase dispersion with vortex-assisted dispersive liquid-liquid microextraction and HPLC with diode array detection.

PubMed

Wang, Xiaozhong; Li, Xuwen; Li, Lanjie; Li, Min; Liu, Ying; Wu, Qian; Li, Peng; Jin, Yongri

2016-05-01

A simple and sensitive method for determination of three aconitum alkaloids and their metabolites in human plasma was developed using matrix solid-phase dispersion combined with vortex-assisted dispersive liquid-liquid microextraction and high-performance liquid chromatography with diode array detection. The plasma sample was directly purified by matrix solid-phase dispersion and the eluate obtained was concentrated and further clarified by vortex-assisted dispersive liquid-liquid microextraction. Some important parameters affecting the extraction efficiency, such as type and amount of dispersing sorbent, type and volume of elution solvent, type and volume of extraction solvent, salt concentration as well as sample solution pH, were investigated in detail. Under optimal conditions, the proposed method has good repeatability and reproducibility with intraday and interday relative standard deviations lower than 5.44 and 5.75%, respectively. The recoveries of the aconitum alkaloids ranged from 73.81 to 101.82%, and the detection limits were achieved within the range of 1.6-2.1 ng/mL. The proposed method offered the advantages of good applicability, sensitivity, simplicity, and feasibility, which makes it suitable for the determination of trace amounts of aconitum alkaloids in human plasma samples. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Small angle x ray scattering studies of reverse micelles in supercritical fluids

NASA Astrophysics Data System (ADS)

Pfund, D. M.; Fulton, J. L.

1994-10-01

The nature of aggregates formed in a supercritical fluid determines its solvent power and selectivity. Small angle X ray scattering (SAXS) is a powerful tool for studying the properties of aggregates with sizes in the 10(angstrom) to 200(angstrom) range. It is also useful in studying those interparticle interactions which operate over a similar distance. The authors have used SAXS to examine the aggregates formed in pure fluids, in mixtures and in fluid/surfactant/water systems. The scattered intensity as a function of angle depends on the geometry, polydispersity, X ray contrast, and interaction strength of the particles as well as on the phase behavior of the system. In this paper the authors present the results of modeling the X-ray scattering from AOT/water reverse micelles in supercritical propane and in propane/carbon dioxide mixtures. They examine the effect of dilution with CO2 anti-solvent on the phase behavior of the system and on the strength of intermicellar attractions. A better understanding of these systems must be obtained before the applications of supercritical reverse micelle systems to extractions, reactions, and enhanced oil recovery can be fully developed.

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.

Doxycycline hyclate-loaded bleached shellac in situ forming microparticle for intraperiodontal pocket local delivery.

PubMed

Phaechamud, Thawatchai; Chanyaboonsub, Nuttapong; Setthajindalert, Orn

2016-10-10

Bleached shellac (BS) is a water-insoluble polyester resin made up of sesquiterpenoid acids esterified with hydroxy aliphatic acids. In this study, BS dissolved in N-methyl pyrrolidone (NMP), dimethyl sulfoxide (DMSO) and 2-pyrrolidone was used as the internal phase of oil in oil emulsion using olive oil emulsified with glyceryl monostearate (GMS) as the external phase of in situ forming microparticles (ISM). Doxycycline hyclate (DH)-loaded BS ISMs were tested for emulsion stability, viscosity, rheology, transformation into microparticles, syringeability, drug release, surface topography, in vitro degradation and antimicrobial activities against Staphylococcus aureus, Streptococcus mutans and Porphyromonas gingivalis. All emulsions exhibited pseudoplastic flow and notably low syringeability force. Slower transformation from emulsion into microparticles of ISM prepared with 2-pyrrolidone was owing to slower solvent exchange of this solvent which promoted less porous structure of obtained BS matrix microparticles. The system containing 2-pyrrolidone exhibited a higher degradability than that prepared with DMSO. Developed DH-loaded BS ISMs exhibited a sustainable drug release for 47days with Fickian diffusion and effectively inhibited P. gingivalis, S. mutans and S. aureus. Therefore a DH-loaded BS ISM using olive oil containing GMS as the external phase and 2-pyrrolidone as a solvent was a suitable formulation for periodontitis treatment. Copyright © 2016 Elsevier B.V. All rights reserved.

First-principles prediction of the effects of temperature and solvent selection on the dimerization of benzoic acid.

PubMed

Pham, Hieu H; Taylor, Christopher D; Henson, Neil J

2013-01-24

We introduce a procedure of quantum chemical calculations (B3P86/6-31G**) to study carboxylic acid dimerization and its correlation with temperature and properties of the solvent. Benzoic acid is chosen as a model system for studying dimerization via hydrogen bonding. Organic solvents are simulated using the self-consistent reaction field (SCRF) method with the polarized continuum model (PCM). The cyclic dimer is the most stable structure both in gas phase and solution. Dimer mono- and dihydrates could be found in the gas phase if acid molecules are in contact with water vapor. However, the formation of these hydrated conformers is very limited and cyclic dimer is the principal conformer to coexist with monomer acid in solution. Solvation of the cyclic dimer is more favorable compared to other complexes, partially due to the diminishing of hydrogen bonding capability and annihilation of dipole moments. Solvents have a strong effect on inducing dimer dissociation and this dependence is more pronounced at low dielectric constants. By accounting for selected terms in the total free energy of solvation, the solvation entropy could be incorporated to predict the dimer behavior at elevated temperatures. The temperature dependence of benzoic acid dimerization obtained by this technique is in good agreement with available experimental measurements, in which a tendency of dimer to dissociate is observed with increased temperatures. In addition, dimer breakup is more sensitive to temperature in low dielectric environments rather than in solvents with a higher dielectric constant.

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

NASA Astrophysics Data System (ADS)

Minnick, David L.

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

Process for radioisotope recovery and system for implementing same

DOEpatents

Meikrantz, David H [Idaho Falls, ID; Todd, Terry A [Aberdeen, ID; Tranter, Troy J [Idaho Falls, ID; Horwitz, E Philip [Naperville, IL

2009-10-06

A method of recovering daughter isotopes from a radioisotope mixture. The method comprises providing a radioisotope mixture solution comprising at least one parent isotope. The at least one parent isotope is extracted into an organic phase, which comprises an extractant and a solvent. The organic phase is substantially continuously contacted with an aqueous phase to extract at least one daughter isotope into the aqueous phase. The aqueous phase is separated from the organic phase, such as by using an annular centrifugal contactor. The at least one daughter isotope is purified from the aqueous phase, such as by ion exchange chromatography or extraction chromatography. The at least one daughter isotope may include actinium-225, radium-225, bismuth-213, or mixtures thereof. A liquid-liquid extraction system for recovering at least one daughter isotope from a source material is also disclosed.

Process for radioisotope recovery and system for implementing same

DOEpatents

Meikrantz, David H.; Todd, Terry A.; Tranter, Troy J.; Horwitz, E. Philip

2007-01-02

A method of recovering daughter isotopes from a radioisotope mixture. The method comprises providing a radioisotope mixture solution comprising at least one parent isotope. The at least one parent isotope is extracted into an organic phase, which comprises an extractant and a solvent. The organic phase is substantially continuously contacted with an aqueous phase to extract at least one daughter isotope into the aqueous phase. The aqueous phase is separated from the organic phase, such as by using an annular centrifugal contactor. The at least one daughter isotope is purified from the aqueous phase, such as by ion exchange chromatography or extraction chromatography. The at least one daughter isotope may include actinium-225, radium-225, bismuth-213, or mixtures thereof. A liquid-liquid extraction system for recovering at least one daughter isotope from a source material is also disclosed.

Application of dispersive liquid-liquid microextraction coupled with vortex-assisted hydrophobic magnetic nanoparticles based solid-phase extraction for determination of aflatoxin M1 in milk samples by sensitive micelle enhanced spectrofluorimetry.

PubMed

Amoli-Diva, Mitra; Taherimaslak, Zohreh; Allahyari, Mehdi; Pourghazi, Kamyar; Manafi, Mohammad Hanif

2015-03-01

An efficient, simple and fast low-density solvent based dispersive liquid-liquid microextraction (LDS-DLLME) followed by vortex-assisted dispersive solid phase extraction (VA-D-SPE) has been developed as a new approach for extraction and preconcentration of aflatoxin M1 in milk samples prior to its micelle enhanced spectrofluorimetic determination. In this LDS-DLLME coupled VA-D-SPE method, milk samples were first treated with methanol/water (80:20, v/v) after removing the fat layer. This solvent was directly used as the dispersing solvent in DLLME along with using 1-heptanol (as a low-density solvent with respect to water) as the extracting solvent. In VA-D-SPE approach, hydrophobic oleic acid modified Fe3O4 nanoparticles were used to retrieve the analyte from the DLLME step. It is considerably that the target of VA-D-SPE was 1-heptanol rather than the aflatoxin M1 directly. The main parameters affecting the efficiency of LDS-DLLME and VA-D-SPE procedures and signal enhancement of aflatoxin M1 were investigated and optimized. Under the optimum conditions, the method was linear in the range from 0.02 to 200 µg L(-1) with the correlation coefficient (R(2)) of 0.9989 and detection limit of 13 ng L(-1). The intra-day precision was 2.9 and 4.3% and the inter-day precision was 2.1 and 3.3% for concentration of 2 and 50 µg L(-1) respectively. The developed method was applied for extraction and preconcentration of AFM1 in three commercially available milk samples and the results were compared with the official AOAC method. Copyright © 2014 Elsevier B.V. All rights reserved.

Partition of nonionic organic compounds in aquatic systems

USGS Publications Warehouse

Smith, James A.; Witkowski, Patrick J.; Chiou, Cary T.

1988-01-01

In aqueous systems, the distribution of many nonionic organic solutes in soil-sediment, aquatic organisms, and dissolved organic matter can be explained in terms of a partition model. The nonionic organic solute is distributed between water and different organic phases that behave as bulk solvents. Factors such as polarity, composition, and molecular size of the solute and organic phase determine the relative importance of partition to the environmental distribution of the solute. This chapter reviews these factors in the context of a partition model and also examines several environmental applications of the partition model for surface- and ground-water systems.

Selective Template Wetting Routes to Hierarchical Polymer Films: Polymer Nanotubes from Phase-Separated Films via Solvent Annealing.

PubMed

Ko, Hao-Wen; Cheng, Ming-Hsiang; Chi, Mu-Huan; Chang, Chun-Wei; Chen, Jiun-Tai

2016-03-01

We demonstrate a novel wetting method to prepare hierarchical polymer films with polymer nanotubes on selective regions. This strategy is based on the selective wetting abilities of polymer chains, annealed in different solvent vapors, into the nanopores of porous templates. Phase-separated films of polystyrene (PS) and poly(methyl methacrylate) (PMMA), two commonly used polymers, are prepared as a model system. After anodic aluminum oxide (AAO) templates are placed on the films, the samples are annealed in vapors of acetic acid, in which the PMMA chains are swollen and wet the nanopores of the AAO templates selectively. As a result, hierarchical polymer films containing PMMA nanotubes can be obtained after the AAO templates are removed. The distribution of the PMMA nanotubes of the hierarchical polymer films can also be controlled by changing the compositions of the polymer blends. This work not only presents a novel method to fabricate hierarchical polymer films with polymer nanotubes on selective regions, but also gives a deeper understanding in the selective wetting ability of polymer chains in solvent vapors.

Non-ideality by sedimentation velocity of halophilic malate dehydrogenase in complex solvents.

PubMed Central

Solovyova, A; Schuck, P; Costenaro, L; Ebel, C

2001-01-01

We have investigated the potential of sedimentation velocity analytical ultracentrifugation for the measurement of the second virial coefficients of proteins, with the goal of developing a method that allows efficient screening of different solvent conditions. This may be useful for the study of protein crystallization. Macromolecular concentration distributions were modeled using the Lamm equation with the approximation of linear concentration dependencies of the diffusion constant, D = D(o) (1 + k(D)c), and the reciprocal sedimentation coefficient s = s(o)/(1 + k(s)c). We have studied model distributions for their information content with respect to the particle and its non-ideal behavior, developed a strategy for their analysis by direct boundary modeling, and applied it to data from sedimentation velocity experiments on halophilic malate dehydrogenase in complex aqueous solvents containing sodium chloride and 2-methyl-2,4-pentanediol, including conditions near phase separation. Using global modeling for three sets of data obtained at three different protein concentrations, very good estimates for k(s) and s degrees and also for D degrees and the buoyant molar mass were obtained. It was also possible to obtain good estimates for k(D) and the second virial coefficients. Modeling of sedimentation velocity profiles with the non-ideal Lamm equation appears as a good technique to investigate weak inter-particle interactions in complex solvents and also to extrapolate the ideal behavior of the particle. PMID:11566761

Preparation of porphyrins and their metal complexes

DOEpatents

Ellis, Jr., Paul E.; Langdale, Wayne A.

1997-01-01

A hydroxyl-containing pyrrolic compound having a hydroxyl group or a hydroxyl-containing group in the 2-position, optionally substituted in the beta positions, is condensed in an acidified two immiscible phase solvent system to produce excellent yields of the corresponding porphyrin or metal porphyrin.

Preparation of porphyrins and their metal complexes

DOEpatents

Ellis, P.E. Jr.; Langdale, W.A.

1997-08-19

A hydroxyl-containing pyrrolic compound having a hydroxyl group or a hydroxyl-containing group in the 2-position, optionally substituted in the beta positions, is condensed in an acidified two immiscible phase solvent system to produce excellent yields of the corresponding porphyrin or metal porphyrin.

Preparative isolation and purification of theaflavins and catechins by high-speed countercurrent chromatography.

PubMed

Wang, Kunbo; Liu, Zhonghua; Huang, Jian-an; Dong, Xinrong; Song, Lubing; Pan, Yu; liu, Fang

2008-05-15

High-speed countercurrent chromatography (HSCCC) has been applied for the separation of theaflavins and catechins. The HSCCC run was carried out with a two-phase solvent system composed of hexane-ethyl acetate-methanol-water-acetic acid (1:5:1:5:0.25, v/v) by eluting the lower aqueous phase at 2 ml/min at 700 rpm. The results indicated that pure theaflavin, theaflavins-3-gallate, theaflavins-3'-gallate and theaflavin-3,3'-digallate could be obtained from crude theaflavins sample and black tea. The structures of the isolated compounds were positively confirmed by (1)H NMR and (13)C NMR, MS analysis, HPLC data and TLC data. Meanwhile, catechins including epigallocatechin gallate, gallocatechin gallate, epicatechin gallate and epigallocatechin were isolated from the aqueous extract of green tea by using the same solvent system. This study developed a modified method combined with enrichment theaflavins method by using HSCCC for separation of four individual theaflavins, especially for better separation of theaflavins monogallates.

A novel dual-valve sequential injection manifold (DV-SIA) for automated liquid-liquid extraction. Application for the determination of picric acid.

PubMed

Skrlíková, Jana; Andruch, Vasil; Sklenárová, Hana; Chocholous, Petr; Solich, Petr; Balogh, Ioseph S

2010-05-07

A novel dual-valve sequential injection system (DV-SIA) for online liquid-liquid extraction which resolves the main problems of LLE utilization in SIA has been designed. The main idea behind this new design was to construct an SIA system by connecting two independent units, one for aqueous-organic mixture flow and the second specifically for organic phase flow. As a result, the DV-SIA manifold consists of an Extraction unit and a Detection unit. Processing a mixture of aqueous-organic phase in the Extraction unit and a separated organic phase in the Detection unit solves the problems associated with the change of phases having different affinities to the walls of the Teflon tubing used in the SI-system. The developed manifold is a simple, user-friendly and universal system built entirely from commercially available components. The system can be used for a variety of samples and organic solvents and is simple enough to be easily handled by operators less familiar with flow systems. The efficiency of the DV-SIA system is demonstrated by the extraction of picric acid in the form of an ion associate with 2-[2-(4-methoxy-phenylamino)-vinyl]-1,3,3-trimethyl-3H-indolium reagent, with subsequent spectrophotometric detection. The suggested DV-SIA concept can be expected to stimulate new experiments in analytical laboratories and can be applied to the elaboration of procedures for the determination of other compounds extractable by organic solvents. It could thus form a basis for the design of simple, single-purpose commercial instruments used in LLE procedures. 2010 Elsevier B.V. All rights reserved.

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

DOE PAGES

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

2016-04-27

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

Simultaneously 'pushing' and 'pulling' graphene oxide into low-polar solvents through a designed interface.

PubMed

Liu, Zhen; Liu, Jingquan; Wang, Yichao; Razal, Joselito M; Francis, Paul S; Biggs, Mark J; Barrow, Colin J; Yang, Wenrong

2018-08-03

Dispersing graphene oxide (GO) in low-polar solvents can realize a perfect self-assembly with functional molecules and application in removal of organic impurities that only dissolve in low-polar solvents. The surface chemistry of GO plays an important role in its dispersity in these solvents. The direct transfer of hydrophilic GO into low-polar solvents, however, has remained an experimental challenge. In this study, we design an interface to transfer GO by simultaneously 'pushing and pulling' the nanosheets into low-polar solvents. Our approach is outstanding due to the ability to obtain monolayers of chemically reduced GO (CRGO) with designed surface properties in the organic phase. Using the transferred GO or CRGO dispersions, we have fabricated GO/fullerene nanocomposites and assessed the ability of CRGOs for dye adsorption. We hope our work can provide a universal approach for the phase transfer of other nanomaterials.

Lyotropic liquid crystal engineering moving beyond binary compositional space - ordered nanostructured amphiphile self-assembly materials by design.

PubMed

van 't Hag, Leonie; Gras, Sally L; Conn, Charlotte E; Drummond, Calum J

2017-05-22

Ordered amphiphile self-assembly materials with a tunable three-dimensional (3D) nanostructure are of fundamental interest, and crucial for progressing several biological and biomedical applications, including in meso membrane protein crystallization, as drug and medical contrast agent delivery vehicles, and as biosensors and biofuel cells. In binary systems consisting of an amphiphile and a solvent, the ability to tune the 3D cubic phase nanostructure, lipid bilayer properties and the lipid mesophase is limited. A move beyond the binary compositional space is therefore required for efficient engineering of the required material properties. In this critical review, the phase transitions upon encapsulation of more than 130 amphiphilic and soluble additives into the bicontinuous lipidic cubic phase under excess hydration are summarized. The data are interpreted using geometric considerations, interfacial curvature, electrostatic interactions, partition coefficients and miscibility of the alkyl chains. The obtained lyotropic liquid crystal engineering design rules can be used to enhance the formulation of self-assembly materials and provides a large library of these materials for use in biomedical applications (242 references).

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.

APPI-MS: Effects of mobile phases and VUV lamps on the detection of PAH compounds

PubMed Central

Short, Luke Chandler; Cai, Sheng-Suan; Syage, Jack A.

2009-01-01

The technique of atmospheric pressure photoionization (APPI) has several advantages over electrospray ionization (ESI) and atmospheric pressure chemical ionization (APCI), including efficient ionization of non-polar or low charge affinity compounds, reduced susceptibility to ion suppression, high sensitivity, and large linear dynamic range. These benefits are greatest at low flow rates (i.e., ≤100 μL/min), while at a higher flow, photon absorption and ion-molecule reactions become significant. Under certain circumstances, APPI signal and S/N have been observed to excel at higher flow, which may be due to a non-photoionzation mechanism. To better understand APPI at higher flow rates, we have selected three lamps (Xe, Kr and Ar) and four mobile phases typical for reverse-phase, high-pressure liquid chromatography: acetonitrile, methanol, (1:1) acetonitrile:water and (1:1) methanol:water. As test compounds, three polyaromatic hydrocarbons are studied: benzo[a]pyrene, indeno[1,2,3-c,d]pyrene and benz[a]anthracene. We find that solvent photoabsorption cross-section is not the only parameter in explaining relative signal intensity, but that solvent photo-ion chemistry can also play a significant role. Three conclusions from this investigation are: (i) Methanol photoionization leads to protonated methanol clusters that can result in chemical ionization of analyte molecule; (ii) Use of the Ar lamp often results in greater signal and S/N; (iii) Acetonitrile photoionization is less efficient and resulting clusters are too strongly bound to efficiently chemically ionize the analyte, so that analyte ion formation is dominated by direct photoionization. PMID:17188507

APPI-MS: effects of mobile phases and VUV lamps on the detection of PAH compounds.

PubMed

Short, Luke Chandler; Cai, Sheng-Suan; Syage, Jack A

2007-04-01

The technique of atmospheric pressure photoionization (APPI) has several advantages over electrospray ionization (ESI) and atmospheric pressure chemical ionization (APCI), including efficient ionization of nonpolar or low charge affinity compounds, reduced susceptibility to ion suppression, high sensitivity, and large linear dynamic range. These benefits are greatest at low flow rates (i.e.,

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.

Solvent effect on the intermolecular proton transfer of the Watson and Crick guanine-cytosine and adenine-thymine base pairs: a polarizable continuum model study.

PubMed

Romero, Eduardo E; Hernandez, Florencio E

2018-01-03

Herein we present our results on the study of the double proton transfer (DPT) mechanism in the adenine-thymine (AT) and guanine-cytosine (GC) base pairs, both in gas phase and in solution. The latter was modeled using the polarizable continuum method (PCM) in different solvents. According to our DFT calculations, the DPT may occur for both complexes in a stepwise mechanism in condensate phase. In gas phase only the GC base pair exhibits a concerted DPT mechanism. Using the Wigner's tunneling corrections to the transition state theory we demonstrate that such corrections are important for the prediction of the rate constants of both systems in gas and in condensate phase. We also show that (i) as the polarity of the medium decreases the equilibrium constant of the DPT reaction increases in both complexes, and (ii) that the equilibrium constant in the GC complex is four orders of magnitude larger than in AT. This observation suggests that the spontaneous mutations in DNA base pairs are more probable in GC than in AT.

Extraction and characterization of polysaccharides from Semen Cassiae by microwave-assisted aqueous two-phase extraction coupled with spectroscopy and HPLC.

PubMed

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

2016-06-25

A novel and rapid method for simultaneous extraction and separation of the different polysaccharides from Semen Cassiae (SC) was developed by microwave-assisted aqueous two-phase extraction (MAATPE) in a one-step procedure. Using ethanol/ammonium sulfate system as a multiphase solvent, the effects of MAATPE on the extraction of polysaccharides from SC such as the composition of the ATPS, extraction time, temperature and solvent-to-material ratio were investigated by UV-vis analysis. Under the optimum conditions, the yields of polysaccharides were 4.49% for the top phase, 8.80% for the bottom phase and 13.29% for total polysaccharides, respectively. Compared with heating solvent extraction and ultrasonic assisted extraction, MAATPE exhibited the higher extraction yields in shorter time. Fourier-transform infrared spectra showed that two polysaccharides extracted from SC to the top and bottom phases by MAATPE were different from each other in their chemical structures. Through acid hydrolysis and PMP derivatization prior to HPLC, analytical results by indicated that a polysaccharide of the top phases was a relatively homogeneous homepolysaccharide composed of dominant gucose glucose while that of the bottom phase was a water-soluble heteropolysaccharide with multiple components of glucose, xylose, arabinose, galactose, mannose and glucuronic acid. Molar ratios of monosaccharides were 95.13:4.27:0.60 of glucose: arabinose: galactose for the polysaccharide from the top phase and 62.96:14.07:6.67: 6.67:5.19:4.44 of glucose: xylose: arabinose: galactose: mannose: glucuronic acid for that from the bottom phase, respectively. The mechanism for MAATPE process was also discussed in detail. MAATPE with the aid of microwave and the selectivity of the ATPS not only improved yields of the extraction, but also obtained a variety of polysaccharides. Hence, it was proved as a green, efficient and promising alternative to simultaneous extraction of polysaccharides from SC. Copyright © 2016 Elsevier Ltd. All rights reserved.

Experiment on the treatment of waste extraction solvent from the molybdenum-99 process

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

Hsien-Ming Hsiao; Chang-Liang Hu; Kuang-Li Chien

2013-07-01

In the Mo-99 (Molybdenum-99) isotope extraction test process for radiopharmaceutical applications, organic solvent is used to extract Mo-99 from an irradiated UO{sub 2} dissolution. The extraction solvent was stored when the test work was stopped. A total of about 120 liters of waste solvent was stored at INER (Institute of Nuclear Energy Research, Taiwan). The extraction solvent consisted of 5% di-(2-ethylhexyl)-phosphoric acid (D2EHPA) and kerosene. The radionuclides found in the waste solvent include Cs-137, Am-241, Tc-99, and Sr-90, which give off gross alpha and beta radioactivity of 1898 and 471 Bq/ml, respectively. This study aims to remove radionuclides from themore » waste solvent using sodium carbonate and sodium hydroxide solutions in different concentrations. After mixing the waste solvent with the alkaline solution followed by settling, a third phase other than organic and aqueous phase appeared which is expected due to the saponification reaction. The experimental results showed that increasing the number of washing and the alkaline solution concentration could enhance the radionuclides removal rate. An optimal removal method was proposed using 2 M Na{sub 2}CO{sub 3} solution twice followed by 1 M NaOH solution one time for the third phase generated early in the mixing stages. The remaining gross alpha and beta radioactivity of the treated organic solvent was 2 and 3 Bq/ml, respectively. The treated solvent could be stabilized by ashing at 500 deg. C and then immobilized. The alkaline solution would be neutralized by hydrochloric or nitric acid and then treated using a variety of adsorbents or bone char via adsorption to remove nuclides to meet the wastewater discharge limitation. (authors)« less

Zone fluidics for measurement of octanol-water partition coefficient of drugs.

PubMed

Wattanasin, Panwadee; Saetear, Phoonthawee; Wilairat, Prapin; Nacapricha, Duangjai; Teerasong, Saowapak

2015-02-20

A novel zone fluidics (ZF) system for the determination of the octanol-water partition coefficient (Pow) of drugs was developed. The ZF system consisted of a syringe pump with a selection valve, a holding column, a silica capillary flow-cell and an in-line spectrophotometer. Exact microliter volumes of solvents (octanol and phosphate buffer saline) and a solution of the drug, sandwiched between air segments, were sequentially loaded into the vertically aligned holding column. Distribution of the drug between the aqueous and octanol phases occurred by the oscillation movement of the syringe pump piston. Phase separation occurred due to the difference in densities. The liquid zones were then pushed into the detection flow cell. In this method, absorbance measurements in only one of the phase (octanol or aqueous) were employed, which together with the volumes of the solvents and pure drug sample, allowed the calculation of the Pow. The developed system was applied to the determination of the Pow of some common drugs. The log (Pow) values agreed well with a batch method (R(2)=0.999) and literature (R(2)=0.997). Standard deviations for intra- and inter-day analyses were both less than 0.1log unit. This ZF system provides a robust and automated method for screening of Pow values in the drug discovery process. Copyright © 2014 Elsevier B.V. All rights reserved.

Brush-Like Polymers: New Design Platforms for Soft, Dry Materials with Unique Property Relations

NASA Astrophysics Data System (ADS)

Daniel, William Francis McKemie, Jr.

Elastomers represent a unique class of engineering materials due to their light weight, low cost, and desirable combination of softness (105 -107 Pa) and large extensibilities (up to 1000%). Despite these advantages, there exist applications that require many times softer modulus, greater extensibility, and stronger strain hardening for the purpose of mimicking the mechanical properties of systems such as biological tissues. Until recently, only liquid-filled gels were suitable materials for such applications, including soft robotics and implants. A considerable amount of work has been done to create gels with superior properties, but despite unique strengths they also suffer from unique weaknesses. This class of material displays fundamental limitations in the form of heterogeneous structures, solvent loss and phase transitions at extreme temperatures, and loss of liquid fraction upon high deformations. In gels the solvent fraction also introduces a large solvent/polymer interaction parameter which must be carefully considered when designing the final mechanical properties. These energetic considerations further exaggerate the capacity for inconstant mechanical properties caused by fluctuations of the solvent fraction. In order to overcome these weaknesses, a new platform for single component materials with low modulus (<105 Pa) must be developed. Single component systems do not suffer from compositional changes over time and display more stable performance in a wider variety of temperatures and humidity conditions. A solvent-free system also has the potential to be homogeneous which replaces the large energetic interactions with comparatively small architectural interaction parameters. If a solvent-free alternative to liquid-filled gels is to be created, we must first consider the fundamental barrier to softer elastomers, i.e. entanglements - intrinsic topological restrains which define a lower limit of modulus ( 105 Pa). These entanglements are determined by chemistry specific parameters (repeat unit volume and Kuhn segment size) in the polymer liquid (melt) prior to crosslinking. Previous solvent free replacements for gels include elastomers end-linked in semidilute conditions. These materials are generated through crosslinking telechelic polymer chains in semidilute solutions at the onset of chain overlap. At such low polymer concentrations entanglements are greatly diluted and once the resulting gel is dried it creates a supersoft and super-elastic network. Although such methods have successfully generated materials with moduli below the 105 Pa limit and high extensibilities ( 1000%) they present their own limitations. Firstly, the semidilute crosslinking methods uses an impractically large volume of solvent which is unattractive in industry. Second, producing and crosslinking large monodisperse telechelic chains is a nontrivial process leading to large uncertainties in the final network architecture and properties. Specifically, telechelics have a distribution of end-to-end distances and in semidilute solutions with extremely low fraction of chain ends the crosslink reaction is diffusion limited, very slow, and imprecise. In order to achieve a superior solvent-free platform, we propose alteration of mechanical properties through the architectural disentanglement of brush-like polymer structures. In recent year there has been an increase in the synthetic conditions and crosslinking schemes available for producing brush-like structures. This makes brush-like materials an attractive alternative to more restrictive methods such as end-linking. Standard networks have one major control factor outside of chemistry, the network stand length. Brush-like architectures are created from long strands with regularly grafted side chains creating three characteristic length scales which may be independently manipulated. In collaboration with M. Rubinstein, we have utilized bottlebrush polymer architectures (a densely grafted brush-like polymer) to experimentally verify theoretical predictions of disentangled bottlebrush melts. By attaching well-defined side chains onto long polymer backbones, individual polymer strands are separated in space (similar to dilution with solvent) accompanied by a comparatively small increase in the rigidity of the strands. The end result is an architectural disentangled melt with an entanglement plateau modulus as much as three orders of magnitude lower than typical linear polymers and a broadly expanded potential for extensibility once crosslinked.

Controlled assembly of nanoparticle structures: spherical and toroidal superlattices and nanoparticle-coated polymeric beads.

PubMed

Isojima, Tatsushi; Suh, Su Kyung; Vander Sande, John B; Hatton, T Alan

2009-07-21

The emulsion droplet solvent evaporation method has been used to prepare nanoclusters of monodisperse magnetite nanoparticles of varying morphologies depending on the temperature and rate of solvent evaporation and on the composition (solvent, presence of polymer, nanoparticle concentration, etc.) of the emulsion droplets. In the absence of a polymer, and with increasing solvent evaporation temperatures, the nanoparticles formed single- or multidomain crystalline superlattices, amorphous spherical aggregates, or toroidal clusters, as determined by the energetics and dynamics of the solvent evaporation process. When polymers that are incompatible with the nanoparticle coatings were included in the emulsion formulation, monolayer- and multilayer-coated polymer beads and partially coated Janus beads were prepared; the nanoparticles were expelled by the polymer as its concentration increased on evaporation of the solvent and accumulated on the surfaces of the beads in a well-ordered structure. The precise number of nanoparticle layers depended on the polymer/magnetic nanoparticle ratio in the oil droplet phase parent emulsion. The magnetic nanoparticle superstructures responded to the application of a modest magnetic field by forming regular chains with alignment of nonuniform structures (e.g., toroids and Janus beads) that are in accord with theoretical predictions and with observations in other systems.

A polyacrylamide-based silica stationary phase for the separation of carbohydrates using alcohols as the weak eluent in hydrophilic interaction liquid chromatography.

PubMed

Cai, Jianfeng; Cheng, Lingping; Zhao, Jianchao; Fu, Qing; Jin, Yu; Ke, Yanxiong; Liang, Xinmiao

2017-11-17

A hydrophilic interaction liquid chromatography (HILIC) stationary phase was prepared by a two-step synthesis method, immobilizing polyacrylamide on silica sphere particles. The stationary phase (named PA, 5μm dia) was evaluated using a mixture of carbohydrates in HILIC mode and the column efficiency reached 121,000Nm -1 . The retention behavior of carbohydrates on PA stationary phase was investigated with three different organic solvents (acetonitrile, ethanol and methanol) employed as the weak eluent. The strongest hydrophilicity of PA stationary phase was observed in both acetonitrile and methanol as the weak eluent, when compared with another two amide stationary phases. Attributing to its high hydrophilicity, three oligosaccharides (xylooligosaccharide, fructooligosaccharide and chitooligosaccharides) presented good retention on PA stationary phase using alcohols/water as mobile phase. Finally, PA stationary phase was successfully applied for the purification of galactooligosaccharides and saponins of Paris polyphylla. It is feasible to use safer and cheaper alcohols to replace acetonitrile as the weak eluent for green analysis and purification of polar compounds on PA stationary phase. Copyright © 2017. Published by Elsevier B.V.

Formation of Nanofibrous Matrices, Three-Dimensional Scaffolds, and Microspheres: From Theory to Practice

PubMed Central

Ma, Chi

2017-01-01

Nanofibrous architecture presents unique biophysical cues to facilitate cellular responses and is considered an indispensable feature of a biomimetic three-dimensional (3D) scaffold and cell carrier. While electrospinning is a widely used method to prepare natural extracellular matrix-like nanofibers, it faces significant challenges to incorporate nanofibrous architecture into well-defined macroporous 3D scaffolds or injectable microspheres. Here we report a nonelectrospinning approach that is effective at generating nanofibers from a variety of synthetic and natural biodegradable polymers and integrating these nanofibers into (1) 3D scaffolds with constructive geometry and designed internal macropore structures; and (2) injectable microspheres. Our approach to generating polymer nanofibers is based on the control of polymer–solvent interaction parameter χp-s. We obtained the χp-s and solvent composition phase diagrams of different temperatures according to the Flory–Huggins classic lattice model and the Hildebrand-Scott solubility parameter equation. A critical polymer–solvent interaction parameter χcrit was introduced as a criterion to predict phase separation and nanofiber formation. To test the effectiveness of our approach, a total of 15 widely used biodegradable polymers were selected and successfully fabricated into nanofibrous matrices. Furthermore, macroporous nanofibrous 3D scaffolds with complex architecture and nanofibrous injectable microspheres were generated from those biodegradable polymers by combining our method with other processes. Our approach is universally effective to fabricate nanofibrous matrices from any polymeric materials. This work, therefore, greatly expands our ability to design appropriate biomimetic 3D scaffolds and injectable cell carriers for advanced regenerative therapies. PMID:27923327

Rapid analysis of water- and fat-soluble vitamins by electrokinetic chromatography with polymeric micelle as pseudostationary phase.

PubMed

Ni, Xinjiong; Xing, Xiaoping; Cao, Yuhua; Cao, Guangqun

2014-11-28

A novel polymeric micelle, formed by random copolymer poly (stearyl methacrylate-co-methacrylic acid) (P(SMA-co-MAA)) has been used as pseudostationary phase (PSP) in electrokinetic chromatography (EKC) for simultaneous and rapid determination of 11 kinds of water- and fat-soluble vitamins in this work. The running buffer consisting of 1% (w/v) P(SMA-co-MAA), 10% (v/v) 1-butanol, 20% (v/v) acetonitrile, and 30 mM Palitzsch buffer solution (pH 9.2) was applied to improve the selectivity and efficiency, as well as to shorten analysis time. 1-Butanol and acetonitrile as the organic solvent modifiers played the most important roles for rapid separation of these vitamins. The effects of organic solvents on microstructure of the polymeric micelle were investigated. The organic solvents swell the polymeric micelle by three folds, lower down the surface charge density and enhance the microenviromental polarity of the polymeric micelle. The 11 kinds of water- and fat-soluble vitamins could be baseline separated within 13 min. The method was applied to determine water- and fat-soluble vitamins in commercial vitamin sample; the recoveries were between 93% and 111% with the relative standard derivations (RSDs) less than 5%. The determination results matched the label claim. Copyright © 2014 Elsevier B.V. All rights reserved.

Modelling the crystallization of the globular proteins

NASA Astrophysics Data System (ADS)

Shiryayev, Andrey S.

Crystallization of globular proteins has become a very important subject in recent yearn. However there is still no understanding of the particular conditions that lead to the crystallization. Since nucleation of a crystalline droplet is the critical step toward the formation of the solid phase from the supersaturated solution, this is the focus of current studies. In this work we use different approaches to investigate the collective behavior of a system of globular proteins. Especially we focused on the models which have a metastable critical point, because this reflects the properties of solutions of globular proteins. The first approach is a continuum model of globular proteins. This model was first presented by Talanquer and Oxtoby and is based on the van der Waals theory. The model can have either a stable or a metastable critical point. For the system with the metastable critical point we studied the behavior of the free energy barrier to nucleation; we found that along particular pathways the barrier to nucleation has a minimim around the critical point. As well, the number of molecules in the critical cluster was found to diverge as one approaches the critical point, though most of the molecules are in the fluid tail of the droplet. Our results are an extension of earlier work [17, 7]. The properties of the solvent affect the behavior of the solution. In our second approach, we proposed a model that takes into account the contribution of the solvent free energy to the free energy of the globular proteins. We show that one can map the phase diagram of a repulsive hard core plus attractive square well interacting system to the same system particles in the solvent environment. In particular we show that this leads to phase diagrams with upper critical points, lower critical points and even closed loops with both upper and lower critical points, similar to the one found before [10]. For systems with interaction different from the square well, in the presence of the solvent this mapping procedure can be a first approximation to understand the phase diagram. The final part of this work is dedicated to the behavior of sickle hemoglobin. While the fluid behavior of the HbS molecules can be approximately explained by the uniform interparticle potential, this model fails to describe the polymerization process and the particular structure of fibers. We develop an anisotropic "patchy" model to describe some features of the HbS polymerization process. To determine the degree of polymerization of the system a "patchy" order parameter was defined. Monte Carlo simulations for the simple two-patch model was performed and reveal the possibility of obtaining chains that can be considered as one dimensional crystals.

A microfluidic device for open loop stripping of volatile organic compounds.

PubMed

Cvetković, Benjamin Z; Dittrich, Petra S

2013-03-01

The detection of volatile organic compounds is of great importance for assessing the quality of water. In this contribution, we describe a miniaturized stripping device that allows fast online detection of organic solvents in water. The core component is a glass microfluidic chip that facilitates the creation of an annular-flowing stream of water and nitrogen gas. Volatile compounds are transferred efficiently from the water into the gas phase along the microfluidic pathway at room temperature within less than 5 s. Before exiting the microchip, the liquid phase is separated from the enriched gas phase by incorporating side capillaries through which the hydrophilic water phase is withdrawn. The gas phase is conveniently collected at the outlet reservoir by tubing. Finally, a semiconductor gas sensor analyzes the concentration of (volatile) organic compounds in the nitrogen gas. The operation and use of the stripping device is demonstrated for the organic solvents THF, 1-propanol, toluene, ethylbenzene, benzaldehyde, and methanol. The mobile, inexpensive, and continuously operating system with liquid flow rates in the low range of microliters per minute can be connected to other detectors or implemented in chemical production line for process control.

Structure and reactions in some amphiphilic association systems

NASA Astrophysics Data System (ADS)

Guo, Rong

1999-06-01

The partial determinations of phase diagrams for some typical surfactants, such as SDS, CTAB and Triton X-100, give the basic aggregated states of the surfactant systems. In the micellar solutions, the diffusion coefficients of some surfactant association systems are determined by the cyclic voltammetry without any probe and used to describe the phase structure. (1) The first CMC, which represents the formation of spherical micelles, and the second CMC, which represents the transformation from spherical to rod-like micelles, are measured. The first and the second CMC are 8.0 x 10-3 mol. L -1 and 5.6 x 10-3 mol. L-1 for SDS, 8.9 x 10-4 mol. L-1 and 2.1 x 10-2 mol. L-1 for CTAB, and 3.2 x 10 -4 mol. L-1 and 1.3 x 10-3 mol. L-1 for Triton X-100, respectively. (2) The addition of polar additives, such as ethanol and benzyl alcohol (BA) in SDS micelles, or hexanol in Triton X-100 micelles, increases the diffusion coefficients and diffusion activation energy, decreases the micropolarity of the micelles with different shape, and causes the transformation from rod-like micelles to spherical ones or from spherical micelles to bicontinuous structure. (3) The isotropic region, which connects to the water comer in the phase diagram, is probably not an area of a single O/W structure, but an area with three different structures---the rod structure, spherical structure and the bicontinuous one. In the lyotropic liquid crystalline phase, the measurements of the small angle X-ray diffraction indicate that the structure parameters, such as interlayer spacing and water penetration, are related to the compositions of the surfactant association systems. The lamellar liquid crystal has a high water penetration but the hexagonal liquid crystal only has a water penetration about 0.05. Some surfactant association systems have been applied in the hydrotrope action of vitamin C (VC) and preparation of nanoparticles, respectively. Vitamin C (VC) can be used as hydrotrope agent in the cationic surfactant CTAB system with various co-surfactants: n-pentanol, n-octanol, n-valeric acid, and n-caproic acid, but not in SDS or Triton X-100 systems. Presence of VC stabilizes both W/O and O/W microemulsions but destabilizes the lamellar liquid crystalline phase. Hence, the "phase transition" from the lamellar liquid crystalline phase to the isotropic phase of O/W, W/O and bicontinuous structure phase occurs with the addition of VC. The hydrotropic action of VC has been used in sunscreens to increase the solubility of sunscreen E 557. The UV absorption spectra of E557 in various media surprisingly had a dependence on the colloid structure. A new method, the preparation of water-soluble nanoparticles, has been found by employing the effect of the penetration of solvent from water layer to amphiphilic layer in lamellar liquid crystals on the solubility of inorganic salts. Water-insoluble nanoparticles have been synthesized by the reaction of two water-soluble inorganic salts in the lamellar liquid crystal. The particle size is less than 10nm and can be controlled by the thickness of the solvent layer in the lamellar liquid crystal. The lamellar liquid crystalline phase of the Triton X-100/decanol/water system has been chosen as a medium because of its large lamellar liquid crystal region and its stability when inorganic salts are added.

Application of molecularly imprinted polymer based matrix solid phase dispersion for determination of fluoroquinolones, tetracyclines and sulfonamides in meat.

PubMed

Wang, Geng Nan; Zhang, Lei; Song, Yi Ping; Liu, Ju Xiang; Wang, Jian Ping

2017-10-15

In this study, a type of novel mixed-template molecularly imprinted polymer was synthesized that was able to recognize 8 fluoroquinolones, 8 sulfonamides and 4 tetracyclines simultaneously with recoveries higher than 92%. Then the polymer was used to develop a matrix solid phase dispersion method for simultaneous extraction of the 20 drugs in pork followed by determination with ultra performance liquid chromatography. During the experiments, the MMIP amount, washing solvent and elution solvent were optimized respectively. The limits of detection of this method for the 20 drugs in pork were in the range of 0.5-3.0ngg -1 , and the intra-day and inter-day recoveries from the fortified blank samples were in the range of 74.5%-102.7%. Therefore, this method could be used as a rapid, simple, specific and sensitive method for multi-determination of the residues of the three classes of drugs in meat. Copyright © 2017 Elsevier B.V. All rights reserved.

A New Method to Grow SiC: Solvent-Laser Heated Floating Zone

NASA Technical Reports Server (NTRS)

Woodworth, Andrew A.; Neudeck, Philip G.; Sayir, Ali

2012-01-01

The solvent-laser heated floating zone (solvent-LHFZ) growth method is being developed to grow long single crystal SiC fibers. The technique combines the single crystal fiber growth ability of laser heated floating zone with solvent based growth techniques (e.g. traveling solvent method) ability to grow SiC from the liquid phase. Initial investigations reported in this paper show that the solvent-LHFZ method readily grows single crystal SiC (retains polytype and orientation), but has a significant amount of inhomogeneous strain and solvent rich inclusions.

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...

NEPTUNIUM SOLVENT EXTRACTION PROCESS

DOEpatents

Dawson, L.R.; Fields, P.R.

1959-10-01

The separation of neptunium from an aqueous solution by solvent extraction and the extraction of neptunium from the solvent solution are described. Neptunium is separated from an aqueous solution containing tetravalent or hexavalent neptunium nitrate, nitric acid, and a nitrate salting out agent, such as sodium nitrate, by contacting the solution with an organic solvent such as diethyl ether. Subsequently, the neptunium nitrate is extracted from the organic solvent extract phase with water.

Modeling the effects of pH and ionic strength on swelling of anionic polyelectrolyte gels

NASA Astrophysics Data System (ADS)

Drozdov, A. D.; deClaville Christiansen, J.

2015-07-01

A constitutive model is developed for the elastic response of an anionic polyelectrolyte gel under swelling in water with an arbitrary pH and an arbitrary molar fraction of dissolved monovalent salt. A gel is treated as a three-phase medium consisting of a solid phase (polymer network), solvent (water), and solute (mobile ions). Transport of solvent and solute is thought of as their diffusion through the polymer network accelerated by an electric field formed by mobile and fixed ions and accompanied by chemical reactions (dissociation of functional groups attached to polymer chains and formation of ion pairs between bound charges and mobile counter-ions). Constitutive equations are derived by means of the free energy imbalance inequality for an arbitrary three-dimensional deformation with finite strains. These relations are applied to analyze equilibrium swelling diagrams on poly(acrylic acid) gel, poly(methacrylic acid) gel, and three composite hydrogels under water uptake in a bath (i) with a fixed molar fraction of salt and varied pH, and (ii) with a fixed pH and varied molar fraction of salt. To validate the ability of the model to predict observations quantitatively, material constants are found by matching swelling curves under one type of experimental conditions and results of simulation are compared with experimental data in the other type of tests.

Solvent extraction system for plutonium colloids and other oxide nano-particles

DOEpatents

Soderholm, Lynda; Wilson, Richard E; Chiarizia, Renato; Skanthakumar, Suntharalingam

2014-06-03

The invention provides a method for extracting plutonium from spent nuclear fuel, the method comprising supplying plutonium in a first aqueous phase; contacting the plutonium aqueous phase with a mixture of a dielectric and a moiety having a first acidity so as to allow the plutonium to substantially extract into the mixture; and contacting the extracted plutonium with second a aqueous phase, wherein the second aqueous phase has a second acidity higher than the first acidity, so as to allow the extracted plutonium to extract into the second aqueous phase. The invented method facilitates isolation of plutonium polymer without the formation of crud or unwanted emulsions.

An Integrated, Low Temperature Process to Capture and Sequester Carbon Dioxide from Industrial Emissions

NASA Astrophysics Data System (ADS)

Wendlandt, R. F.; Foremski, J. J.

2013-12-01

Laboratory experiments show that it is possible to integrate (1) the chemistry of serpentine dissolution, (2) capture of CO2 gas from the combustion of natural gas and coal-fired power plants using aqueous amine-based solvents, (3) long-term CO2 sequestration via solid phase carbonate precipitation, and (4) capture solvent regeneration with acid recycling in a single, continuous process. In our process, magnesium is released from serpentine at 300°C via heat treatment with ammonium sulfate salts or at temperatures as low as 50°C via reaction with sulfuric acid. We have also demonstrated that various solid carbonate phases can be precipitated directly from aqueous amine-based (NH3, MEA, DMEA) CO2 capture solvent solutions at room temperature. Direct precipitation from the capture solvent enables regenerating CO2 capture solvent without the need for heat and without the need to compress the CO2 off gas. We propose that known low-temperature electrochemical methods can be integrated with this process to regenerate the aqueous amine capture solvent and recycle acid for dissolution of magnesium-bearing mineral feedstocks and magnesium release. Although the direct precipitation of magnesite at ambient conditions remains elusive, experimental results demonstrate that at temperatures ranging from 20°C to 60°C, either nesquehonite Mg(HCO3)(OH)●2H2O or a double salt with the formula [NH4]2Mg(CO3)2●4H2O or an amorphous magnesium carbonate precipitate directly from the capture solvent. These phases are less desirable for CO2 sequestration than magnesite because they potentially remove constituents (water, ammonia) from the reaction system, reducing the overall efficiency of the sequestration process. Accordingly, the integrated process can be accomplished with minimal energy consumption and loss of CO2 capture and acid solvents, and a net generation of 1 to 4 moles of H2O/6 moles of CO2 sequestered (depending on the solid carbonate precipitate and amount of produced H2 and O2 gas reacted to produce heat and water). Features of the integrated process include the following: 1) the four separate processes have compatible chemistry, enabling design of an integrated, continuous process scheme for CO2 capture and sequestration; 2) all 4 stages of the process can be conducted at ambient or slightly elevated temperatures; 3) precipitating carbonate directly from the capture solvent eliminates the need for costly CO2 gas compression; and 4) recycling the acid used for serpentine dissolution and the solvent used for CO2 capture reduces feed stock costs.

Communication: Cosolvency and cononsolvency explained in terms of a Flory-Huggins type theory

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

Dudowicz, Jacek, E-mail: dudowicz@jfi.uchicago.edu; Freed, Karl F.; Douglas, Jack F.

2015-10-07

Standard Flory-Huggins (FH) theory is utilized to describe the enigmatic cosolvency and cononsolvency phenomena for systems of polymers dissolved in mixed solvents. In particular, phase boundaries (specifically upper critical solution temperature spinodals) are calculated for solutions of homopolymers B in pure solvents and in binary mixtures of small molecule liquids A and C. The miscibility (or immiscibility) patterns for the ternary systems are classified in terms of the FH binary interaction parameters (χ{sub αβ}) and the ratio r = ϕ{sub A}/ϕ{sub C} of the concentrations ϕ{sub A} and ϕ{sub C} of the two solvents. The trends in miscibility are comparedmore » to those observed for blends of random copolymers (A{sub x}C{sub 1−x}) with homopolymers (B) and to those deduced for A/B/C solutions of polymers B in liquid mixtures of small molecules A and C that associate into polymeric clusters (A{sub p}C{sub q}){sub i}, (i = 1, 2, …, ∞). Although the classic FH theory is able to explain cosolvency and cononsolvency phenomena, the theory does not include a consideration of the mutual association of the solvent molecules and the competitive association between the solvent molecules and the polymer. These interactions can be incorporated in refinements of the FH theory, and the present paper provides a foundation for such extensions for modeling the rich thermodynamics of polymers in mixed solvents.« less

Through the looking glass: Unraveling the network structure of coal

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

Gregory, D. M.; Stec, D. F.; Botto, R. E.

1999-12-23

Since the original idea by Sanada and Honda of treating coal as a three-dimensional cross-linked network, coal structure has been probed by monitoring ingress of solvents using traditional volumetric or gravimetric methods. However, using these techniques has allowed only an indirect observation of the swelling process. More recently, the authors have developed magnetic resonance microscopy (MRM) approaches for studying solvent ingress in polymeric systems, about which fundamental aspects of the swelling process can be deduced directly and quantitatively. The aim of their work is to utilize solvent transport and network response parameters obtained from these methods to assess fundamental propertiesmore » of the system under investigation. Polymer and coal samples have been studied to date. Numerous swelling parameters measured by magnetic resonance microscopy are found to correlate with cross-link density of the polymer network under investigation. Use of these parameters to assess the three-dimensional network structure of coal is discussed.« less

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.

Pseudolatex preparation using a novel emulsion-diffusion process involving direct displacement of partially water-miscible solvents by distillation.

PubMed

Quintanar-Guerrero, D; Allémann, E; Fessi, H; Doelker, E

1999-10-25

Pseudolatexes were obtained by a new process based on an emulsification-diffusion technique involving partially water-miscible solvents. The preparation method consisted of emulsifying an organic solution of polymer (saturated with water) in an aqueous solution of a stabilizing agent (saturated with solvent) using conventional stirrers, followed by direct solvent distillation. The technique relies on the rapid displacement of the solvent from the internal into the external phase which thereby provokes polymer aggregation. Nanoparticle formation is believed to occur because rapid solvent diffusion produces regions of local supersaturation near the interface, and nanoparticles are formed due to the ensuing interfacial phase transformations and polymer aggregation that occur in these interfacial domains. Using this method, it was possible to prepare pseudolatexes of biodegradable and non-biodegradable polymers such as poly(D,L-lactic acid) and poly(epsilon-caprolactone), Eudragit E, cellulose acetate phthalate, cellulose acetate trimellitate using ethyl acetate or 2-butanone as partially water-miscible solvents and poly(vinyl alcohol) or poloxamer 407 as stabilizing agent. A transition from nano- to microparticles was observed at high polymer concentrations. At concentrations above 30% w/v of Eudragit E in ethyl acetate or cellulose acetate phthalate in 2-butanone only microparticles were obtained. This behaviour was attributed to decreased transport of polymer molecules into the aqueous phase.

Quantum and Statistical Mechanics Applied to Singlet Carbenes, Pericyclic Reactions, and Condensed Phase Phenomena

NASA Astrophysics Data System (ADS)

Evanseck, Jeffrey Donald

The completed research covers a broad range of theoretical applications in organic chemistry. It is divided into three chapters which covers the chemistry of singlet carbenes (Chapter 1), substituent effects in pericyclic rearrangements (Chapter 2), and the effects of solvent on the reactivity of organic reactions (Chapter 3). The selectivity between 1,2- and 1,4-intramolecular additions to restricted diene systems has been investigated. A decrease in activation energy for the intramolecular cycloaddition is noted for systems which approach the idealized geometry found with intermolecular addition of carbenes to olefins. Direct substitution at the carbene site dramatically effects the predicted activation barriers for 1,2-hydrogen shifts. An excellent correlation between the activation energy and a substituents sigma_sp {rm R}{rm o} parameters has been demonstrated. The long standing problem of orbital alignment influences on the selectivity of 1,2-hydrogen arrangements shows significant geometric distortions, yet has little influence on the rates of singlet alkylcarbene rearrangements. The exo-selectivities observed for 1,2-shifts in rigid systems are explained by torsional and steric interactions which develop in the transition structures. Substituent effects on pericyclic reactions have been computed for several conrotatory and disrotatory electrocyclizations. The six-electron disrotatory electrocyclization of 1-substituted hexatrienes displays a strong electronic component in determining stereoselectivity, despite incredible steric interference. The eight-electron conrotatory electrocyclization transition structure of 1-substituted octatetraene has an unusual helical transition structure which does not differentiate between substituent position. The effects of solvents on the acidity differences between E and Z esters has supplemented earlier ab initio quantum mechanical results on the enhanced acidity of Meldrum's acid. Monte Carlo simulations predict a preferential stabilization of the E isomer in both acetonitrile and aqueous solutions. The rates of intramolecular Diels-Alder reactions are compared to recent experimental work and predictions of different solvent systems are made.

Determination of sulfonamides and trimethoprim using high temperature HPLC with simultaneous temperature and solvent gradient.

PubMed

Giegold, Sascha; Teutenberg, Thorsten; Tuerk, Jochen; Kiffmeyer, Thekla; Wenclawiak, Bernd

2008-10-01

A fast HPLC method for the analysis of eight selected sulfonamides (SA) and trimethoprim has been developed with the use of high temperature HPLC. The separation could be achieved in less than 1.5 min on a 50 mm sub 2 microm column with simultaneous solvent and temperature gradient programming. Due to the lower viscosity of the mobile phase and the increased mass transfer at higher temperatures, the separation could be performed on a conventional HPLC system obtaining peak widths at half height between 0.6 and 1.3 s.

KSC-00pp0104

NASA Image and Video Library

2000-01-25

At Launch Complex 34, the Six-Phase Soil Heating site that is involved in a groundwater cleanup project can be seen. The project involves the Department of Defense, Environmental Protection Agency, Department of Energy and NASA. Concentrations of trichloroethylene solvent have been identified in the soil at the complex as a result of cleaning methods for rocket parts during the Apollo Program, which used the complex, in the 60s. The group formed the Interagency NDAPL Consortium (IDC) to study three contamination cleanup technologies: Six-Phase Soil Heating, Steam Injection and In Situ Oxidation with Potassium Permanganate. All three methods may offer a way to remove the contaminants in months instead of decades. In the background is the block house for the complex. KSC hosted a two-day conference that presented information and demonstrations of the three technologies being tested at the site

KSC00pp0104

NASA Image and Video Library

2000-01-25

At Launch Complex 34, the Six-Phase Soil Heating site that is involved in a groundwater cleanup project can be seen. The project involves the Department of Defense, Environmental Protection Agency, Department of Energy and NASA. Concentrations of trichloroethylene solvent have been identified in the soil at the complex as a result of cleaning methods for rocket parts during the Apollo Program, which used the complex, in the 60s. The group formed the Interagency NDAPL Consortium (IDC) to study three contamination cleanup technologies: Six-Phase Soil Heating, Steam Injection and In Situ Oxidation with Potassium Permanganate. All three methods may offer a way to remove the contaminants in months instead of decades. In the background is the block house for the complex. KSC hosted a two-day conference that presented information and demonstrations of the three technologies being tested at the site

Groundwater cleanup demonstrations at Complex 34, CCAS

NASA Technical Reports Server (NTRS)

2000-01-01

At Launch Complex 34, the Six-Phase Soil Heating site that is involved in a groundwater cleanup project can be seen. The project involves the Department of Defense, Environmental Protection Agency, Department of Energy and NASA. Concentrations of trichloroethylene solvent have been identified in the soil at the complex as a result of cleaning methods for rocket parts during the Apollo Program, which used the complex, in the 60s. The group formed the Interagency NDAPL Consortium (IDC) to study three contamination cleanup technologies: Six-Phase Soil Heating, Steam Injection and In Situ Oxidation with Potassium Permanganate. All three methods may offer a way to remove the contaminants in months instead of decades. In the background is the block house for the complex. KSC hosted a two-day conference that presented information and demonstrations of the three technologies being tested at the site.

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

Jenkins, T.F.; Thorne, P.G.; Myers, K.F.

Salting-out solvent extraction (SOE) was compared with cartridge and membrane solid-phase extraction (SPE) for preconcentration of nitroaromatics, nitramines, and aminonitroaromatics prior to determination by reversed-phase high-performance liquid chromatography. The solid phases used were manufacturer-cleaned materials, Porapak RDX for the cartridge method and Empore SDB-RPS for the membrane method. Thirty-three groundwater samples from the Naval Surface Warfare Center, Crane, Indiana, were analyzed using the direct analysis protocol specified in SW846 Method 8330, and the results were compared with analyses conducted after preconcentration using SOE with acetonitrile, cartridge-based SPE, and membrane-based SPE. For high-concentration samples, analytical results from the three preconcentration techniquesmore » were compared with results from the direct analysis protocol; good recovery of all target analytes was achieved by all three pre-concentration methods. For low-concentration samples, results from the two SPE methods were correlated with results from the SOE method; very similar data was obtained by the SOE and SPE methods, even at concentrations well below 1 microgram/L.« less

Comparison of solvent extraction and solid-phase extraction for the determination of polychlorinated biphenyls in transformer oil.

PubMed

Mahindrakar, A N; Chandra, S; Shinde, L P

2014-01-01

Solid-phase extraction (SPE) of nine polychlorinated biphenyls (PCBs) from transformer oil samples was evaluated using octadecyl (CI8)-bonded porous silica. The efficiency of SPE of these PCBs was compared with those obtained by solvent extraction with DMSO and hexane. Average recoveries exceeding 95% for these PCBs were obtained via the SPE method using small cartridges containing 100mg of 40 pm CI8-bonded porous silica. The average recovery by solvent extraction with DMSO and hexane exceeded 83%. It was concluded that the recoveries and precision for the solvent extraction of PCBs were poorer than those for the SPE. Copyright © 2013 Elsevier Ltd. All rights reserved.

On the Use of Accelerated Molecular Dynamics to Enhance Configurational Sampling in Ab Initio Simulations.

PubMed

Bucher, Denis; Pierce, Levi C T; McCammon, J Andrew; Markwick, Phineus R L

2011-04-12

We have implemented the accelerated molecular dynamics approach (Hamelberg, D.; Mongan, J.; McCammon, J. A. J. Chem. Phys. 2004, 120 (24), 11919) in the framework of ab initio MD (AIMD). Using three simple examples, we demonstrate that accelerated AIMD (A-AIMD) can be used to accelerate solvent relaxation in AIMD simulations and facilitate the detection of reaction coordinates: (i) We show, for one cyclohexane molecule in the gas phase, that the method can be used to accelerate the rate of the chair-to-chair interconversion by a factor of ∼1 × 10(5), while allowing for the reconstruction of the correct canonical distribution of low-energy states; (ii) We then show, for a water box of 64 H(2)O molecules, that A-AIMD can also be used in the condensed phase to accelerate the sampling of water conformations, without affecting the structural properties of the solvent; and (iii) The method is then used to compute the potential of mean force (PMF) for the dissociation of Na-Cl in water, accelerating the convergence by a factor of ∼3-4 compared to conventional AIMD simulations.(2) These results suggest that A-AIMD is a useful addition to existing methods for enhanced conformational and phase-space sampling in solution. While the method does not make the use of collective variables superfluous, it also does not require the user to define a set of collective variables that can capture all the low-energy minima on the potential energy surface. This property may prove very useful when dealing with highly complex multidimensional systems that require a quantum mechanical treatment.

The Separatory Cylinder: A Novel Solvent Extraction System for the Study of Chemical Equilibrium in Solution.

ERIC Educational Resources Information Center

Cwikel, Dori; And Others

1986-01-01

Dicusses the use of the separatory cylinder in student laboratory experiments for investigating equilibrium distribution of a solute between immiscible phases. Describes the procedures for four sets of experiments of this nature. Lists of materials needed and quantities of reagents are provided. (TW)

Normal and Reversed-Phase Thin Layer Chromatography of Green Leaf Extracts

ERIC Educational Resources Information Center

Sjursnes, Birte Johanne; Kvittingen, Lise; Schmid, Rudolf

2015-01-01

Introductory experiments of chromatography are often conducted by separating colored samples, such as inks, dyes, and plant extracts, using filter paper, chalk, or thin layer chromatography (TLC) plates with various solvent systems. Many simple experiments have been reported. The relationship between normal chromatography and reversed-phase…

Continuous Flow Science in an Undergraduate Teaching Laboratory: Bleach-Mediated Oxidation in a Biphasic System

ERIC Educational Resources Information Center

Kairouz, Vanessa; Collins, Shawn K.

2018-01-01

An undergraduate teaching laboratory experiment involving a continuous flow, bleach-mediated oxidation of aldehydes under biphasic conditions was developed that allowed students to explore concepts of mixing or mass transport, solvent sustainability, biphasic reactions, phase transfer catalysis, and continuous flow chemistry.

Characterization of a Biomimetic Mesophase Composed of Nonionic Surfactants and an Aqueous Solvent.

PubMed

Adrien, V; Rayan, G; Reffay, M; Porcar, L; Maldonado, A; Ducruix, A; Urbach, W; Taulier, N

2016-10-11

We have investigated the physical and biomimetic properties of a sponge (L 3 ) phase composed of pentaethylene glycol monododecyl ether (C 12 E 5 ), a nonionic surfactant, an aqueous solvent, and a cosurfactant. The following cosurfactants, commonly used for solubilizing membrane proteins, were incorporated: n-octyl-β-d-glucopyranoside (β-OG), n-dodecyl-β-d-maltopyranoside (DDM), 4-cyclohexyl-1-butyl-β-d-maltoside (CYMAL-4), and 5-cyclohexyl-1-pentyl-β-d-maltoside (CYMAL-5). Partial phase diagrams of these systems were created. The L 3 phase was characterized using crossed polarizers, diffusion of a fluorescent probe by fluorescence recovery after pattern photobleaching (FRAPP), and freeze fracture electron microscopy (FFEM). By varying the hydration of the phase, we were able to tune the distance between adjacent bilayers. The characteristic distance (d b ) of the phase was obtained from small angle scattering (SAXS/SANS) as well as from FFEM, which yielded complementary d b values. These d b values were neither affected by the nature of the cosurfactant nor by the addition of membrane proteins. These findings illustrate that a biomimetic surfactant sponge phase can be created in the presence of several common membrane protein-solubilizing detergents, thus making it a versatile medium for membrane protein studies.

Summer 2017 Microfluidics Research Report

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

Mcculloch, Quinn

Liquid-liquid Extraction (LLE), also known as solvent extraction, represents a large subset of chemistry where one or more solutes are transferred across an interface between two immiscible liquids. This type of chemistry is used in industrial scale processes to purify solvents, refine ore, process petroleum, treat wastewater, and much more. Although LLE has been successfully employed at the macroscale, where many liters/kgs of species are processed at large flow rates, LLE stands to benefit from lab-on-a-chip technology, where reactions take place quickly and efficiently at the microscale. A device, called a screen contactor, has been invented at Los Alamos Nationalmore » Laboratory (LANL) to perform solvent extraction at the microscale. This invention has been submitted to LANL’s Feynman Center for Innovation, and has been filed for provisional patent under U.S. Patent Application No. 62/483,107 1. The screen contactor consists of a housing that contains two different screen materials, flametreated stainless steel and polyether ether ketone (PEEK) thermoplastic, that are uniquely wetted by either an aqueous or an organic liquid phase, respectively. Liquids in this device flow longitudinally through the screens. The fine pore size of the screens (tens of microns) provide large capillary/adhesional forces while maintaining small hydraulic pressure drops. These physical characteristics are paramount to efficient microscale liquid phase separation. To demonstrate mass transfer using the screen contactor, a well-known chemical system 2 consisting of water and n-decane as solvents and trimethylamine (TEA) as a solute was selected. TEA is basic in water so its concentration can easily be quantified using a digital pH meter and an experimentally determined base dissociation constant. Characterization of this solvent system and its behavior in the screen contactor have been the focus of my research activities this summer. In the following sections, I have detailed experimental results that have been gathered.« less

High drug loading self-microemulsifying/micelle formulation: design by high-throughput formulation screening system and in vivo evaluation.

PubMed

Sakai, Kenichi; Obata, Kouki; Yoshikawa, Mayumi; Takano, Ryusuke; Shibata, Masaki; Maeda, Hiroyuki; Mizutani, Akihiko; Terada, Katsuhide

2012-10-01

To design a high drug loading formulation of self-microemulsifying/micelle system. A poorly-soluble model drug (CH5137291), 8 hydrophilic surfactants (HS), 10 lipophilic surfactants (LS), 5 oils, and PEG400 were used. A high loading formulation was designed by a following stepwise approach using a high-throughput formulation screening (HTFS) system: (1) an oil/solvent was selected by solubility of the drug; (2) a suitable HS for highly loading was selected by the screenings of emulsion/micelle size and phase stability in binary systems (HS, oil/solvent) with increasing loading levels; (3) a LS that formed a broad SMEDDS/micelle area on a phase diagram containing the HS and oil/solvent was selected by the same screenings; (4) an optimized formulation was selected by evaluating the loading capacity of the crystalline drug. Aqueous solubility behavior and oral absorption (Beagle dog) of the optimized formulation were compared with conventional formulations (jet-milled, PEG400). As an optimized formulation, d-α-tocopheryl polyoxyethylene 1000 succinic ester: PEG400 = 8:2 was selected, and achieved the target loading level (200 mg/mL). The formulation formed fine emulsion/micelle (49.1 nm), and generated and maintained a supersaturated state at a higher level compared with the conventional formulations. In the oral absorption test, the area under the plasma concentration-time curve of the optimized formulation was 16.5-fold higher than that of the jet-milled formulation. The high loading formulation designed by the stepwise approach using the HTFS system improved the oral absorption of the poorly-soluble model drug.

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

PubMed

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

2015-11-01

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

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

PubMed

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

2002-01-01

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

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.

Development of green betaine-based deep eutectic solvent aqueous two-phase system for the extraction of protein.

PubMed

Li, Na; Wang, Yuzhi; Xu, Kaijia; Huang, Yanhua; Wen, Qian; Ding, Xueqin

2016-05-15

Six kinds of new type of green betaine-based deep eutectic solvents (DESs) have been synthesized. Deep eutectic solvent aqueous two-phase systems (DES-ATPS) were established and successfully applied in the extraction of protein. Betaine-urea (Be-U) was selected as the suitable extractant. Single factor experiments were carried out to determine the optimum conditions of the extraction process, such as the salt concentration, the mass of DES, the separation time, the amount of protein, the temperature and the pH value. The extraction efficiency could achieve to 99.82% under the optimum conditions. Mixed sample and practical sample analysis were discussed. The back extraction experiment was implemented and the back extraction efficiency could reach to 32.66%. The precision experiment, repeatability experiment and stability experiment were investigated. UV-vis, FT-IR and circular dichroism (CD) spectra confirmed that the conformation of protein was not changed during the process of extraction. The mechanisms of extraction were researched by dynamic light scattering (DLS), the measurement of the conductivity and transmission electron microscopy (TEM). DES-protein aggregates and embraces phenomenon play considerable roles in the separation process. All of these results indicated that betaine-based DES-ATPS may provide a potential substitute new method for the separation of proteins. Copyright © 2016 Elsevier B.V. All rights reserved.

Dielectric Interactions and the Prediction of Retention Times of Pesticides in Supercritical Fluid Chromatography with CO2

NASA Astrophysics Data System (ADS)

Alvarez, Guillermo A.; Baumanna, Wolfram

2005-02-01

A thermodynamic model for the partition of a solute (pesticide) between two immiscible phases, such as the stationary and mobile phases of supercritical fluid chromatography with CO2, is developed from first principles. A key ingredient of the model is the result of the calculation made by Liptay of the energy of interaction of a polar molecule with a dielectric continuum, which represents the solvent. The strength of the interaction between the solute and the solvent, which may be considered a measure of the solvent power, is characterized by a function g = (ɛ - 1)/(2ɛ +1), where ɛ is the dielectric constant of the medium, which is a function of the temperature T and the pressure P. Since the interactions between the nonpolar supercritical CO2 solvent and the slightly polar pesticide molecules are considered to be extremely weak, a regular solution model is appropriate from the thermodynamic point of view. At constant temperature, the model predicts a linear dependence of the logarithm of the capacity factor (lnk) of the chromatographic experiment on the function g = g(P), as the pressure is varied, with a slope which depends on the dipole moment of the solute, dispersion interactions and the size of the solute cavity in the solvent. At constant pressure, once the term containing the g (solvent interaction) factor is subtracted from lnk, a plot of the resulting term against the inverse of temperature yields the enthalpy change of transfer of the solute from the mobile (supercritical CO2) phase to the stationary (adsorbent) phase. The increase in temperature with the consequent large volume expansion of the supercritical fluid lowers its solvent strength and hence the capacity factor of the column (or solute retention time) increases. These pressure and temperature effects, predicted by the model, agree excellently with the experimental retention times of seven pesticides. Beyond a temperature of about 393 K, where the liquid solvent densities approach those of a gas (and hence the solvent strength becomes negligible), a dramatic loss of the retention times of all pesticides is observed in the experiments; this is attributed to desorption of the solute from the stationary phase, as predicted by Le Châtelier's principle for the (exothermic) adsorption process.

Preparative isolation of huperzines A and B from Huperzia serrata by displacement centrifugal partition chromatography.

PubMed

Toribio, Alix; Delannay, Eldra; Richard, Bernard; Plé, Karen; Zèches-Hanrot, Monique; Nuzillard, Jean-Marc; Renault, Jean-Hugues

2007-01-26

The pH-zone refining centrifugal partition chromatography technique was used to separate the two acetylcholinesterase inhibitors huperzines A and B from a crude alkaloid extract of the club moss Huperzia serrata. Complete co-elution of huperzines A and B was initially observed with the well-known methyl tert-butyl ether-acetonitrile-water (4:1:5, v/v/v) solvent system with triethylamine (8mM) as the displacer and methane sulfonic acid (6mM) as the retainer. An efficient biphasic system was designed on the basis of solvent association that provided selectivity in the elution mode: n-heptane/ethyl acetate/n-propanol/water (5:15:35:45, v/v/v/v). Lowering the bridge solvent content (n-propanol) of this system increased the polarity difference between the two phases thus adapting it to the pH-zone refining mode. Thus, the purification of these compounds was achieved using the biphasic system n-heptane/ethyl acetate/n-propanol/water (10:30:15:45, v/v/v/v) with triethylamine (8mM) as the displacer and methane sulfonic acid (6mM) as the retainer.

High-throughput determination of octanol/water partition coefficients using a shake-flask method and novel two-phase solvent system.

PubMed

Morikawa, Go; Suzuka, Chihiro; Shoji, Atsushi; Shibusawa, Yoichi; Yanagida, Akio

2016-01-05

A high-throughput method for determining the octanol/water partition coefficient (P(o/w)) of a large variety of compounds exhibiting a wide range in hydrophobicity was established. The method combines a simple shake-flask method with a novel two-phase solvent system comprising an acetonitrile-phosphate buffer (0.1 M, pH 7.4)-1-octanol (25:25:4, v/v/v; AN system). The AN system partition coefficients (K(AN)) of 51 standard compounds for which log P(o/w) (at pH 7.4; log D) values had been reported were determined by single two-phase partitioning in test tubes, followed by measurement of the solute concentration in both phases using an automatic flow injection-ultraviolet detection system. The log K(AN) values were closely related to reported log D values, and the relationship could be expressed by the following linear regression equation: log D=2.8630 log K(AN) -0.1497(n=51). The relationship reveals that log D values (+8 to -8) for a large variety of highly hydrophobic and/or hydrophilic compounds can be estimated indirectly from the narrow range of log K(AN) values (+3 to -3) determined using the present method. Furthermore, log K(AN) values for highly polar compounds for which no log D values have been reported, such as amino acids, peptides, proteins, nucleosides, and nucleotides, can be estimated using the present method. The wide-ranging log D values (+5.9 to -7.5) of these molecules were estimated for the first time from their log K(AN) values and the above regression equation. Copyright © 2015 Elsevier B.V. All rights reserved.

COORDINATION COMPOUND-SOLVENT EXTRACTION PROCESS FOR URANIUM RECOVERY

DOEpatents

Reas, W.H.

1959-03-10

A method is presented for the separation of uranium from aqueous solutions containing a uranyl salt and thorium. Thc separation is effected by adding to such solutions an organic complexing agent, and then contacting the solution with an organic solvent in which the organic complexing agent is soluble. By use of the proper complexing agent in the proper concentrations uranium will be complexed and subsequently removed in the organic solvent phase, while the thorium remains in the aqueous phase. Mentioned as suitable organic complexing agents are antipyrine, bromoantipyrine, and pyramidon.

How High Pressure Unifies Solvation Processes in Liquid Chromatography.

PubMed

Bocian, Szymon; Škrinjar, Tea; Bolanca, Tomislav; Buszewski, Bogusław

2017-11-01

A series of core-shell-based stationary phases of varying surface chemistry were subjected to solvent adsorption investigation under ultra-HPLC conditions. Acetonitrile and water excess isotherms were measured using a minor disturbance method. It was observed that adsorption of organic solvent is unified under high pressure. Preferential solvation due to specific interactions between the stationary phases and solvent molecules was limited. The obtained results showed that the solvation process is almost independent of surface chemistry, in contrast to HPLC conditions in which specific interactions differentiate solvation processes.

Automated clean-up, separation and detection of polycyclic aromatic hydrocarbons in particulate matter extracts from urban dust and diesel standard reference materials using a 2D-LC/2D-GC system.

PubMed

Ahmed, Trifa M; Lim, Hwanmi; Bergvall, Christoffer; Westerholm, Roger

2013-10-01

A multidimensional, on-line coupled liquid chromatographic/gas chromatographic system was developed for the quantification of polycyclic aromatic hydrocarbons (PAHs). A two-dimensional liquid chromatographic system (2D-liquid chromatography (LC)), with three columns having different selectivities, was connected on-line to a two-dimensional gas chromatographic system (2D-gas chromatography (GC)). Samples were cleaned up by combining normal elution and column back-flush of the LC columns to selectively remove matrix constituents and isolate well-defined, PAH enriched fractions. Using this system, the sequential removal of polar, mono/diaromatic, olefinic and alkane compounds from crude extracts was achieved. The LC/GC coupling was performed using a fused silica transfer line into a programmable temperature vaporizer (PTV) GC injector. Using the PTV in the solvent vent mode, excess solvent was removed and the enriched PAH sample extract was injected into the GC. The 2D-GC setup consisted of two capillary columns with different stationary phase selectivities. Heart-cutting of selected PAH compounds in the first GC column (first dimension) and transfer of these to the second GC column (second dimension) increased the baseline resolutions of closely eluting PAHs. The on-line system was validated using the standard reference materials SRM 1649a (urban dust) and SRM 1975 (diesel particulate extract). The PAH concentrations measured were comparable to the certified values and the fully automated LC/GC system performed the clean-up, separation and detection of PAHs in 16 extracts in less than 24 h. The multidimensional, on-line 2D-LC/2D-GC system eliminated manual handling of the sample extracts and minimised the risk of sample loss and contamination, while increasing accuracy and precision.

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

PubMed

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

2014-05-01

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

Microcapsules and Methods for Making

NASA Technical Reports Server (NTRS)

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

1998-01-01

Methods of forming multi-lamellar microcapsules having alternating layers of hydrophilic and hydrophobic immiscible liquid phases have been developed using different polymer/solvent systems. The methods use liquid-liquid diffusion and simultaneous lateral phase separation, controlled by proper timed-sequence exposures of immiscible phases and low shear mixing, to form narrow size distributions of spherical, multilamellar microcapsules. The use of special formulations of solubilized drugs, surfactants, and polymeric co-surfactants in aqueous vehicles which are dispersed in hydrocarbon solvents containing small quantities of oil, low molecular weight co-surfactants and glycerides that are aqueous insoluble enables the formation of unique microcapsules which can carry large amounts of pharmaceuticals in both aqueous and non-aqueous solvent compartments. The liquid microcapsules are quickly formed in a single step and can include a polymeric outer 'skin' which protects the microcapsules during physical manipulation or exposure to high shear forces. Water-in-oil and oil-in-water microcapsules have been formed both in 1 x g and in microgravity, which contain several types of drugs co-encapsulated within different fluid compartments inside the same microcapsule. Large, spherical multi-lamellar microcapsules have been formed including a cytotoxic drug co-encapsulated with a radiocontrast medium which has advantages for chemoembolization of vascular tumors. In certain cases, crystals of the drug form inside the microcapsules providing zero-order and first order, sustained drug release kinetics.

Capillary liquid chromatography combined with pressurized liquid extraction and dispersive liquid-liquid microextraction for the determination of vitamin E in cosmetic products.

PubMed

Viñas, Pilar; Pastor-Belda, Marta; Campillo, Natalia; Bravo-Bravo, María; Hernández-Córdoba, Manuel

2014-06-01

Capillary liquid chromatography (LC) is used for the determination of tocopherols and tocotrienols in cosmetic products. Dispersive liquid-liquid microextraction (DLLME) allows the analytes to be preconcentrated into a very small volume of organic solvent which is then injected into the chromatograph running at a very low flow rate. Pressurized liquid extraction (PLE) at a high temperature and pressure was used to isolate vitamin E forms from cosmetics. The Taguchi experimental method was used to optimize the factors affecting DLLME. The parameters selected were 2mL of acetonitrile (disperser solvent), 100μL carbon tetrachloride (extraction solvent) and 10mL aqueous solution. A volume of 5μL of the organic phase was injected into the reversed-phase capillary LC system equipped with a diode array detector and using an isocratic mobile phase composed of an 95:5 (v/v) methanol:water mixture at a flow-rate of 20μLmin(-1). Quantification was carried out using aqueous standards and detection limits were in the range 0.1-0.5ngmL(-1), corresponding to 3-15ngg(-1) in the cosmetic sample. The recoveries were in the 87-105% range, with RSDs lower than 7.8%. The method was validated according to international guidelines and using a certified reference material. Copyright © 2014 Elsevier B.V. All rights reserved.

Synthesis and application of mesoporous molecular sieve for miniaturized matrix solid-phase dispersion extraction of bioactive flavonoids from toothpaste, plant, and saliva.

PubMed

Cao, Wan; Cao, Jun; Ye, Li-Hong; Xu, Jing-Jing; Hu, Shuai-Shuai; Peng, Li-Qing

2015-12-01

This article describes the use of the mesoporous molecular sieve KIT-6 as a sorbent in miniaturized matrix solid-phase dispersion (MSPD) in combination with ultra-performance LC for the determination of bioactive flavonoids in toothpaste, Scutellariae Radix, and saliva. In this study, for the first time, KIT-6 was used as a sorbent material for this mode of extraction. Compared with common silica-based sorbents (C18 and activated silica gel), the proposed KIT-6 dispersant with a three-dimensional cubic Ia3d structure and highly ordered arrays of mesoporous channels exhibits excellent adsorption capability of the tested compounds. In addition, several experimental variables, such as the mass ratio of sample to dispersant, grinding time, and elution solvent, were optimized to maximize the extraction efficiency. The proposed analytical method is simple, fast, and entails low consumption of samples, dispersants and elution solvents, thereby meeting "green chemistry" requirements. Under the optimized conditions, the recoveries of three bioactive flavonoids obtained by analyzing the spiked samples were from 89.22 to 101.17%. Also, the LODs and LOQs for determining the analytes were in the range of 0.02-0.04 μg/mL and 0.07-0.13 μg/mL, respectively. Finally, the miniaturized matrix solid-phase dispersion method was successfully applied to the analysis of target solutes in real samples, and satisfactory results were obtained. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Application of the Baxter model for hard-spheres with surface adhesion to SANS data for the U(VI) - HNO{sub 3}, TBP-n-dodecane system.

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

Chiarizia, R.; Nash, K. L.; Jensen, M. P.

2003-11-11

Small-angle neutron scattering (SANS) data for the tri-n-butyl phosphate (TBP)-n-dodecane, HNO{sub 3}-UO{sub 2}(NO{sub 3}){sub 2} solvent extraction system have been interpreted using the Baxter model for hard spheres with surface adhesion. The increase in the scattering intensity in the low Q range observed when increasing amounts of HNO{sub 3} or UO{sub 2}(NO{sub 3}){sub 2} are transferred into the organic phase has been interpreted as arising from interactions between solute particles. The SANS data have been reproduced using a 12--16 {angstrom} diameter of the hard sphere, d{sub hs}, and a 5.6k{sub B}T-7.1k{sub B}T stickiness parameter, {tau}{sup -1}. When in contact withmore » an aqueous phase, TBP in n-dodecane forms small reverse micelles containing three TBP molecules. Upon extraction of water, HNO{sub 3}, and UO{sub 2}(NO{sub 3}){sub 2}, the swollen micelles interact through attractive forces between their polar cores with a potential energy of about 2k{sub B}T and an effective Hamaker constant of about 4k{sub B}T. The intermicellar attraction, under suitable conditions, leads to third-phase formation. Upon phase splitting, most of the solutes in the original organic phase (water, TBP, HNO{sub 3}, and UO{sub 2}(NO{sub 3}){sub 2}) separate in a continuous phase containing interspersed layers of n-dodecane.« less

Synthesis and characterization of low viscosity carbon dioxide binding organic liquids for flue gas clean up

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

Koech, Phillip K.; Malhotra, Deepika; Heldebrant, David J.

2015-01-01

Climate change is partly attributed to global anthropogenic carbon dioxide (CO2) emission to the atmosphere. These environmental effects can be mitigated by CO2 capture, utilization and storage. Alkanolamine solvents, such as monoethanolamine (MEA), which bind CO2 as carbamates or bicarbonate salts are used for CO2 capture in niche applications. These solvents consist of approximately 30 wt% of MEA in water, exhibiting a low, CO2-rich viscosity, fast kinetics and favorable thermodynamics. However, these solvents have low CO2 capacity and high heat capacity of water, resulting in prohibitively high costs of thermal solvent regeneration. Effective capture of the enormous amounts of CO2more » produced by coal-fired plants requires a material with high CO2 capacity and low regeneration energy requirements. To this end, several water-lean transformational solvents systems have been developed in order to reduce these energy penalties. These technologies include nano-material organic hybrids (NOHMs), task-specific, protic and conventional ionic liquids, phase change solvents. As part of an ongoing program in our group, we have developed new water lean transformational solvents known as CO2 binding organic liquids (CO2BOLs) which have the potential to be energy efficient CO2 capture solvents. These solvents, also known as switchable ionic liquids meaning, are organic solvents that can reversibly transform from non- ionic to ionic form and back. The zwitterionic state in these liquids is formed when low polarity non-ionic alkanolguanidines or alkanolamidines react with CO2 or SO2 to form ionic liquids with high polarity. These polar ionic liquids can be thermally converted to the less polar non-ionic solvent by releasing CO2.« less

PH-zone-refining counter-current chromatography with a hydrophilic organic/salt-containing two-phase solvent system for preparative separation of polar alkaloids from natural products.

PubMed

Zou, Denglang; Du, Yurong; Kuang, Jianyuan; Sun, Shihao; Ma, Jianbin; Jiang, Renwang

2018-06-08

This study presents an efficient strategy based on pH-zone-refining counter-current chromatography with a hydrophilic organic/salt-containing two-phase system composed of acetonitrile, sodium chloride and water for preparative separation of polar alkaloids from natural products. Acetonitrile-sodium chloride-water system provides a wider range of polarity for polar alkaloids than classical aqueous two-phase systems. It gets rid of the effect of free hydrogen ion, strong ionic strength, hold low viscosity and the sharp retainer border could be formed easily. So acetonitrile-sodium chloride-water system showed great advantages to pH-zone-refining counter-current chromatography for polar alkaloids. The separation of polar indole alkaloids from toad venom was selected as an example to show the advantage and practicability of this strategy. An optimized acetonitrile-sodium chloride-water (54%:5%:41%, w%) system was applied in this study, where 10 mM triethylamine (TEA) as the retainer and 15 mM hydrochloric acid (HCl) as the eluter were added. As a result, three polar indole alkaloids, including 19 mg of serotonin, 45 mg of 5-Hydroxy-N'-methyl tryptamine, 33 mg of bufotenine were simultaneously separated from 500 mg of 5% ethanol elution fraction of toad venom on macroporous resin chromatography, with the purity of 91.3%, 97.5% and 89.4%, respectively. Their structures were identified by spectroscopic analysis. Copyright © 2018 Elsevier B.V. All rights reserved.

Separation of chlorogenic acid and concentration of trace caffeic acid from natural products by pH-zone-refining countercurrent chromatography.

PubMed

Lu, Yuanyuan; Dong, Genlai; Gu, Yanxiang; Ito, Yoichiro; Wei, Yun

2013-07-01

Chlorogenic acid and caffeic acid were selected as test samples for separation by the pH-zone-refining countercurrent chromatography (CCC). The separation of these test samples was performed with a two-phase solvent system composed of methyl-tert-butyl-ether/acetonitrile/water at a volume ratio of 4:1:5 v/v/v where trifluoroacetic acid (TFA; 8 mM) was added to the organic stationary phase as a retainer and NH4 OH (10 mM) to the aqueous mobile phase as an eluter. Chlorogenic acid was successfully separated from Flaveria bidentis (L.) Kuntze (F. bidentis) and Lonicerae Flos by pH-zone-refining CCC, a slightly polar two-phase solvent system composed of methyl-tert-butyl-ether/acetonitrile/n-butanol/water at a volume ratio of 4:1:1:5 v/v/v/v was selected where TFA (3 mM) was added to the organic stationary phase as a retainer and NH4 OH (3 mM) to the aqueous mobile phase as an eluter. A 16.2 mg amount of chlorogenic acid with the purity of 92% from 1.4 g of F. bidentis, and 134 mg of chlorogenic acid at the purity of 99% from 1.3 g of crude extract of Lonicerae Flos have been obtained. These results suggest that pH-zone-refining CCC is suitable for the isolation of the chlorogenic acid from the crude extracts of F. bidentis and Lonicerae Flos. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Sensitivity of Imaging Materials to Electron Beam Irradiation

DTIC Science & Technology

1991-04-01

solvent/nonsolvent ratio, and in the solid state by applying mechanical stresses. The terms thermochromism , solvatochromism, and mechanochromism have been...these examples, the thermochromic phase transitions that occur in solution are reversible [101. The changes in optical absorption for solutions of 3BCMU...three-dimensional perspective, as would be observed in a monomolecular layer of an LB film. Flanking this view are both a side view (14a) and a front

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.

Low Friction Hull Coatings for Icebreakers. Phase II, Parts I and II. Laboratory and Field Tests

DTIC Science & Technology

1976-02-01

is a hybrid of the above systems . It contains no solvent, can cure at room temperature, is flexible and exhibits good wear characteristics. This...31 Figure I-12 Schematic of Humidity Control System Figure I-13 Effect of Velocity on the Friction Coefficient of...Application of a Conventional Epoxy System and a Vinyl Antifoul Photographs of the USCG Cutter Mackinaw during and after Application of Polyurethane Coating

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.

Graphene-sensitized microporous membrane/solvent microextraction for the preconcentration of cinnamic acid derivatives in Rhizoma Typhonii.

PubMed

Xing, Rongrong; Hu, Shuang; Chen, Xuan; Bai, Xiaohong

2014-09-01

A novel graphene-sensitized microporous membrane/solvent microextraction method named microporous membrane/graphene/solvent synergistic microextraction, coupled with high-performance liquid chromatography and UV detection, was developed and introduced for the extraction and determination of three cinnamic acid derivatives in Rhizoma Typhonii. Several factors affecting performance were investigated and optimized, including the types of graphene and extraction solvent, concentration of graphene dispersed in octanol, sample phase pH, ionic strength, stirring rate, extraction time, extraction temperature, and sample volume. Under optimized conditions, the enrichment factors of cinnamic acid derivatives ranged from 75 to 269. Good linearities were obtained from 0.01 to 10 μg/mL for all analytes with regression coefficients between 0.9927 and 0.9994. The limits of quantification were <1 ng/mL, and satisfactory recoveries (99-104%) and precision (1.1-10.8%) were also achieved. The synergistic microextraction mechanism based on graphene sensitization was analyzed and described. The experimental results showed that the method was simple, sensitive, practical, and effective for the preconcentration and determination of cinnamic acid derivatives in Rhizoma Typhonii. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Preparation of cerium halide solvate complexes

DOEpatents

Vasudevan, Kalyan V; Smith, Nickolaus A; Gordon, John C; McKigney, Edward A; Muenchaussen, Ross E

2013-08-06

Crystals of a solvated cerium(III) halide solvate complex resulted from a process of forming a paste of a cerium(III) halide in an ionic liquid, adding a solvent to the paste, removing any undissolved solid, and then cooling the liquid phase. Diffusing a solvent vapor into the liquid phase also resulted in crystals of a solvated cerium(III) halide complex.

Hydrodynamic effects on phase separation morphologies in evaporating thin films of polymer solutions

NASA Astrophysics Data System (ADS)

Zoumpouli, Garyfalia A.; Yiantsios, Stergios G.

2016-08-01

We examine effects of hydrodynamics on phase separation morphologies developed during drying of thin films containing a volatile solvent and two dissolved polymers. Cahn-Hilliard and Flory-Huggins theories are used to describe the free energy of the phase separating systems. The thin films, considered as Newtonian fluids, flow in response to Korteweg stresses arising due to concentration non-uniformities that develop during solvent evaporation. Numerical simulations are employed to investigate the effects of a Peclet number, defined in terms of system physical properties, as well as the effects of parameters characterizing the speed of evaporation and preferential wetting of the solutes at the gas interface. For systems exhibiting preferential wetting, diffusion alone is known to favor lamellar configurations for the separated phases in the dried film. However, a mechanism of hydrodynamic instability of a short length scale is revealed, which beyond a threshold Peclet number may deform and break the lamellae. The critical Peclet number tends to decrease as the evaporation rate increases and to increase with the tendency of the polymers to selectively wet the gas interface. As the Peclet number increases, the instability moves closer to the gas interface and induces the formation of a lateral segregation template that guides the subsequent evolution of the phase separation process. On the other hand, for systems with no preferential wetting or any other property asymmetries between the two polymers, diffusion alone favors the formation of laterally separated configurations. In this case, concentration perturbation modes that lead to enhanced Korteweg stresses may be favored for sufficiently large Peclet numbers. For such modes, a second mechanism is revealed, which is similar to the solutocapillary Marangoni instability observed in evaporating solutions when interfacial tension increases with the concentration of the non-volatile component. This mechanism may lead to multiple length scales in the laterally phase separated configurations.

The Chemistry of Separations Ligand Degradation by Organic Radical Cations

DOE PAGES

Mezyk, Stephen P.; Horne, Gregory P.; Mincher, Bruce J.; ...

2016-12-01

Solvent based extractions of used nuclear fuel use designer ligands in an organic phase extracting ligand complexed metal ions from an acidic aqueous phase. These extractions will be performed in highly radioactive environments, and the radiation chemistry of all these complexants and their diluents will play a major role in determining extraction efficiency, separation factors, and solvent-recycle longevity. Although there has been considerable effort in investigating ligand damage occurring in acidic water radiolysis conditions, only minimal fundamental kinetic and mechanistic data has been reported for the degradation of extraction ligands in the organic phase. Extraction solvent phases typically use normalmore » alkanes such as dodecane, TPH, and kerosene as diluents. The radiolysis of such diluents produce a mixture of radical cations (R •+), carbon-centered radicals (R •), solvated electrons, and molecular products such as hydrogen. Typically, the radical species will preferentially react with the dissolved oxygen present to produce relatively inert peroxyl radicals. This isolates the alkane radical cation species, R •+ as the major radiolytically-induced organic species that can react with, and degrade, extraction agents in this phase. Here we report on our recent studies of organic radical cation reactions with various ligands. Elucidating these parameters, and combining them with the known acidic aqueous phase chemistry, will allow a full, fundamental, understanding of the impact of radiation on solvent extraction based separation processes to be achieved.« less

The Chemistry of Separations Ligand Degradation by Organic Radical Cations

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

Mezyk, Stephen P.; Horne, Gregory P.; Mincher, Bruce J.

Solvent based extractions of used nuclear fuel use designer ligands in an organic phase extracting ligand complexed metal ions from an acidic aqueous phase. These extractions will be performed in highly radioactive environments, and the radiation chemistry of all these complexants and their diluents will play a major role in determining extraction efficiency, separation factors, and solvent-recycle longevity. Although there has been considerable effort in investigating ligand damage occurring in acidic water radiolysis conditions, only minimal fundamental kinetic and mechanistic data has been reported for the degradation of extraction ligands in the organic phase. Extraction solvent phases typically use normalmore » alkanes such as dodecane, TPH, and kerosene as diluents. The radiolysis of such diluents produce a mixture of radical cations (R •+), carbon-centered radicals (R •), solvated electrons, and molecular products such as hydrogen. Typically, the radical species will preferentially react with the dissolved oxygen present to produce relatively inert peroxyl radicals. This isolates the alkane radical cation species, R •+ as the major radiolytically-induced organic species that can react with, and degrade, extraction agents in this phase. Here we report on our recent studies of organic radical cation reactions with various ligands. Elucidating these parameters, and combining them with the known acidic aqueous phase chemistry, will allow a full, fundamental, understanding of the impact of radiation on solvent extraction based separation processes to be achieved.« less

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.

Improving the efficiency of molecular replacement by utilizing a new iterative transform phasing algorithm

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

He, Hongxing; Fang, Hengrui; Miller, Mitchell D.

2016-07-15

An iterative transform algorithm is proposed to improve the conventional molecular-replacement method for solving the phase problem in X-ray crystallography. Several examples of successful trial calculations carried out with real diffraction data are presented. An iterative transform method proposed previously for direct phasing of high-solvent-content protein crystals is employed for enhancing the molecular-replacement (MR) algorithm in protein crystallography. Target structures that are resistant to conventional MR due to insufficient similarity between the template and target structures might be tractable with this modified phasing method. Trial calculations involving three different structures are described to test and illustrate the methodology. The relationshipmore » of the approach to PHENIX Phaser-MR and MR-Rosetta is discussed.« less

Efficient sample preparation method based on solvent-assisted dispersive solid-phase extraction for the trace detection of butachlor in urine and waste water samples.

PubMed

Aladaghlo, Zolfaghar; Fakhari, Alireza; Behbahani, Mohammad

2016-10-01

In this work, an efficient sample preparation method termed solvent-assisted dispersive solid-phase extraction was applied. The used sample preparation method was based on the dispersion of the sorbent (benzophenone) into the aqueous sample to maximize the interaction surface. In this approach, the dispersion of the sorbent at a very low milligram level was achieved by inserting a solution of the sorbent and disperser solvent into the aqueous sample. The cloudy solution created from the dispersion of the sorbent in the bulk aqueous sample. After pre-concentration of the butachlor, the cloudy solution was centrifuged and butachlor in the sediment phase dissolved in ethanol and determined by gas chromatography with flame ionization detection. Under the optimized conditions (solution pH = 7.0, sorbent: benzophenone, 2%, disperser solvent: ethanol, 500 μL, centrifuged at 4000 rpm for 3 min), the method detection limit for butachlor was 2, 3 and 3 μg/L for distilled water, waste water, and urine sample, respectively. Furthermore, the preconcentration factor was 198.8, 175.0, and 174.2 in distilled water, waste water, and urine sample, respectively. Solvent-assisted dispersive solid-phase extraction was successfully used for the trace monitoring of butachlor in urine and waste water samples. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

3,3',5-Triiodo-L-thyronine-like activity in effluents from domestic sewage treatment plants detected by in vitro and in vivo bioassays

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

Murata, Tomonori; Yamauchi, Kiyoshi

2008-02-01

Thyroid system-disrupting activity in effluents from municipal domestic sewage treatment plants was detected using three in vitro assays and one in vivo assay. Contaminants in the effluents were extracted by solid-phase extraction (SPE) and eluted stepwise with different organic solvents. The majority of the thyroid system-disrupting activity was detected in the dichloromethane/methanol (1/1) fraction after SPE in all three in vitro assays: competitive assays of 3,3',5-[{sup 125}I]triiodo-L-thyronine ([{sup 125}I]T{sub 3}) binding to the plasma protein transthyretin (TTR assay) and thyroid hormone receptor (TR assay) and T{sub 3}-dependent luciferase assay (Luc assay). Subsequent reverse-phase high-performance liquid chromatography (RP-HPLC) of the dichloromethane/methanolmore » (1/1) fraction separated contaminants potent in the TR and Luc assays from those potent in the TTR assay. The contaminants potent in the TR and Luc assays were also potent in an in vivo short-term gene expression assay in Xenopus laevis (Tadpole assay). The present study demonstrated that the effluents from domestic sewage treatment plants contain contaminants with T{sub 3}-like activity of {approx} 10{sup -10} M T{sub 3}-equivalent concentration (T{sub 3}EQ) and that the TR and Luc assays are powerful in vitro bioassays for detecting thyroid system-disrupting activity in effluents. The availability and applicability of these bioassays for screening contaminants with thyroid system-disrupting activity in the water environment are discussed.« less

THE SOLVENT EXTRACTION OF NITROSYLRUTHENIUM BY TRILAURYLAMINE IN NITRATE SYSTEM. Summary Report for the Period, July 1, 1960 to March 31, 1962

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

Skavdahl, R.E.; Mason, E.A.

1962-06-01

An investigation of the solvent extraction characteristics of the nitro and nitrato complexes of nitrosylruthenium in nitric acid- sodium nitrate aqueous media was conducted. As the organic extractant phase, a solution of trilaurylamine (TLA) in toluene was utilized. In addition to the usual process parameter variation tyne of experiment, a rapid dilution type of experiment was used extensively to determine qualitative and semiquantitative results regarding the degree of extractability and concentration of the more extractable species of the nitrato complexes of nitrosylruthenium. It was found that the acids of the tetra-nitrato and pentanitrato complexes were the more extractable species formore » that set of complexes and that the acid of the penta-nitrato complex was the more extractable of the two. It was observed that for freshly prepared solutions, the dinitro complex of nitrosylruthenium was much more extractable than the gross nitrato complexes solutions. Nitro complexes in general, and the dinitro complex in particular, may be the controlling agent in ruthenium decontamination of spent nuclear fuel processed by solvent extraction methods. The experimental results from both sets of complexes could be more meaningfully correlated on the basis of unbound nitric acid concentration in the organic phase than on the basis of nitric acid concentration in the aqueous phase. The extraction of nitric acid by TLA from nitric acid-sodium nitrate aqueous solutions was investigated and the results correlated on the basis of activity of the undissociated nitric acid in the aqueous phase. (auth)« less

Feasibility of Surfactant-Free Supported Emulsion Liquid Membrane Extraction

NASA Technical Reports Server (NTRS)

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

2001-01-01

Supported emulsion liquid membrane (SELM) is an effective means to conduct liquid-liquid extraction. SELM extraction is particularly attractive for separation tasks in the microgravity environment where density difference between the solvent and the internal phase of the emulsion is inconsequential and a stable dispersion can be maintained without surfactant. In this research, dispersed two-phase flow in SELM extraction is modeled using the Lagrangian method. The results show that SELM extraction process in the microgravity environment can be simulated on earth by matching the density of the solvent and the stripping phase. Feasibility of surfactant-free SELM (SFSELM) extraction is assessed by studying the coalescence behavior of the internal phase in the absence of the surfactant. Although the contacting area between the solvent and the internal phase in SFSELM extraction is significantly less than the area provided by regular emulsion due to drop coalescence, it is comparable to the area provided by a typical hollow-fiber membrane. Thus, the stripping process is highly unlikely to become the rate-limiting step in SFSELM extraction. SFSELM remains an effective way to achieve simultaneous extraction and stripping and is able to eliminate the equilibrium limitation in the typical solvent extraction processes. The SFSELM design is similar to the supported liquid membrane design in some aspects.

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

PubMed

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

2007-09-07

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

Integrating a post-column makeup pump into preparative supercritical fluid chromatography systems to address stability and recovery issues during purifications.

PubMed

Bajpai, Lakshmikant; Naidu, Harshavardhan; Asokan, Kathiravan; Shaik, Khaja Mohiddin; Kaspady, Mahammed; Arunachalam, Piramanayagam; Wu, Dauh-Rurng; Mathur, Arvind; Sarabu, Ramakanth

2017-08-18

Purification of many pharmaceutical compounds by supercritical fluid chromatography (SFC) has always been challenging because of degradation of compound during the isolation step in the presence of acidic or basic modifiers in the mobile phase. Stability of such acid or base-sensitive compounds could be improved by post-column addition of a solvent containing base or acid modifier as counter ion through a make-up pump respectively to neutralize the compound fraction without affecting the resolution. One such case study has been presented in this work where the stability of a base-sensitive compound was addressed by the addition of acidic co-solvent through the make-up pump. Details of this setup and the investigation of degradation of the in-house base-sensitive compound are discussed in this paper. In addition, poor retentivity and low recovery of many non-polar compounds in SFC eluting under low co-solvent percentage is another major concern. Even though the desired separation could be achieved with low percentage of co-solvent, it's difficult to get the proper recovery after purification due to precipitation of the sample and significant aerosol formation inside the cyclone. We have demonstrated the first-time use of a post-column make-up pump on SFC 350 system to introduce additional solvent prior to cyclone to avoid the precipitation, reduce the aerosol formation and thus improve the recovery of non-polar compounds eluting under less than 10% of co-solvent. Copyright © 2017 Elsevier B.V. All rights reserved.

Solvent effects on the fluorescence and effective three-photon absorption of a Zn(II)-[meso-tetrakis(4-octyloxyphenyl)porphyrin

NASA Astrophysics Data System (ADS)

Wan, Yong; Xue, Yuxiong; Sheng, Ning; Rui, Guanghao; Lv, Changgui; He, Jun; Gu, Bing; Cui, Yiping

2018-06-01

The fluorescence and effective three-photon absorption (3PA) properties of Zn(II)-[meso-tetrakis(4-octyloxyphenyl)porphyrin] (labeled Zn(II)-porphyrin) dissolved in three different polar solvents were systematically investigated. The electrochemical and photophysical properties of Zn(II)-porphyrin were investigated by 1H NMR spectra, IR spectra, mass spectroscopy, and electronic absorption spectra. The fluorescence emission of Zn(II)-porphyrin in three different solvents excited at the wavelengths of 420 nm (Soret band) and 550 nm (Q-band) were analyzed. By performing Z-scan experiments with femtosecond laser pulses at a wavelength of 800 nm, the effective 3PA process of Zn(II)-porphyrin in three different solvents was observed and the underlying mechanism was discussed in detail. It is found that the fluorescence spectra slightly depend on the polarity of the solvent. Interestingly, the effective 3PA properties of Zn(II)-porphyrin strongly depend on the solvent polarity. The lower the solvent polarity is, the larger effective 3PA cross-section is. Low polar solvents are beneficial to applications of Zn(II)-porphyrin in optical limiting, photodynamic therapy, etc.

Aqueous Biphasic Systems for the Synthesis of Formates by Catalytic CO2 Hydrogenation: Integrated Reaction and Catalyst Separation for CO2 -Scrubbing Solutions.

PubMed

Scott, Martin; Blas Molinos, Beatriz; Westhues, Christian; Franciò, Giancarlo; Leitner, Walter

2017-03-22

Aqueous biphasic systems were investigated for the production of formate-amine adducts by metal-catalyzed CO 2 hydrogenation, including typical scrubbing solutions as feedstocks. Different hydrophobic organic solvents and ionic liquids could be employed as the stationary phase for cis-[Ru(dppm) 2 Cl 2 ] (dppm=bis-diphenylphosphinomethane) as prototypical catalyst without any modification or tagging of the complex. The amines were found to partition between the two phases depending on their structure, whereas the formate-amine adducts were nearly quantitatively extracted into the aqueous phase, providing a favorable phase behavior for the envisaged integrated reaction/separation sequence. The solvent pair of methyl isobutyl carbinol (MIBC) and water led to the most practical and productive system and repeated use of the catalyst phase was demonstrated. The highest single batch activity with a TOF av of approximately 35 000 h -1 and an initial TOF of approximately 180 000 h -1 was achieved in the presence of NEt 3 . Owing to higher stability, the highest productivities were obtained with methyl diethanolamine (Aminosol CST 115) and monoethanolamine (MEA), which are used in commercial scale CO 2 -scrubbing processes. Saturated aqueous solutions (CO 2 overpressure 5-10 bar) of MEA could be converted into the corresponding formate adducts with average turnover frequencies up to 14×10 3  h -1 with an overall yield of 70 % based on the amine, corresponding to a total turnover number of 150 000 over eleven recycling experiments. This opens the possibility for integrated approaches to carbon capture and utilization. © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

Aqueous Biphasic Systems for the Synthesis of Formates by Catalytic CO2 Hydrogenation: Integrated Reaction and Catalyst Separation for CO2‐Scrubbing Solutions

PubMed Central

Scott, Martin; Blas Molinos, Beatriz; Westhues, Christian

2017-01-01

Abstract Aqueous biphasic systems were investigated for the production of formate–amine adducts by metal‐catalyzed CO2 hydrogenation, including typical scrubbing solutions as feedstocks. Different hydrophobic organic solvents and ionic liquids could be employed as the stationary phase for cis‐[Ru(dppm)2Cl2] (dppm=bis‐diphenylphosphinomethane) as prototypical catalyst without any modification or tagging of the complex. The amines were found to partition between the two phases depending on their structure, whereas the formate–amine adducts were nearly quantitatively extracted into the aqueous phase, providing a favorable phase behavior for the envisaged integrated reaction/separation sequence. The solvent pair of methyl isobutyl carbinol (MIBC) and water led to the most practical and productive system and repeated use of the catalyst phase was demonstrated. The highest single batch activity with a TOFav of approximately 35 000 h−1 and an initial TOF of approximately 180 000 h−1 was achieved in the presence of NEt3. Owing to higher stability, the highest productivities were obtained with methyl diethanolamine (Aminosol CST 115) and monoethanolamine (MEA), which are used in commercial scale CO2‐scrubbing processes. Saturated aqueous solutions (CO2 overpressure 5–10 bar) of MEA could be converted into the corresponding formate adducts with average turnover frequencies up to 14×103 h−1 with an overall yield of 70 % based on the amine, corresponding to a total turnover number of 150 000 over eleven recycling experiments. This opens the possibility for integrated approaches to carbon capture and utilization. PMID:28103428

Coupled-cluster based approach for core-level states in condensed phase: Theory and application to different protonated forms of aqueous glycine

DOE PAGES

Sadybekov, Arman; Krylov, Anna I.

2017-07-07

A theoretical approach for calculating core-level states in condensed phase is presented. The approach is based on equation-of-motion coupled-cluster theory (EOMCC) and effective fragment potential (EFP) method. By introducing an approximate treatment of double excitations in the EOM-CCSD (EOM-CC with single and double substitutions) ansatz, we address poor convergence issues that are encountered for the core-level states and significantly reduce computational costs. While the approximations introduce relatively large errors in the absolute values of transition energies, the errors are systematic. Consequently, chemical shifts, changes in ionization energies relative to reference systems, are reproduced reasonably well. By using different protonation formsmore » of solvated glycine as a benchmark system, we show that our protocol is capable of reproducing the experimental chemical shifts with a quantitative accuracy. The results demonstrate that chemical shifts are very sensitive to the solvent interactions and that explicit treatment of solvent, such as EFP, is essential for achieving quantitative accuracy.« less

Coupled-cluster based approach for core-level states in condensed phase: Theory and application to different protonated forms of aqueous glycine

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

Sadybekov, Arman; Krylov, Anna I.

A theoretical approach for calculating core-level states in condensed phase is presented. The approach is based on equation-of-motion coupled-cluster theory (EOMCC) and effective fragment potential (EFP) method. By introducing an approximate treatment of double excitations in the EOM-CCSD (EOM-CC with single and double substitutions) ansatz, we address poor convergence issues that are encountered for the core-level states and significantly reduce computational costs. While the approximations introduce relatively large errors in the absolute values of transition energies, the errors are systematic. Consequently, chemical shifts, changes in ionization energies relative to reference systems, are reproduced reasonably well. By using different protonation formsmore » of solvated glycine as a benchmark system, we show that our protocol is capable of reproducing the experimental chemical shifts with a quantitative accuracy. The results demonstrate that chemical shifts are very sensitive to the solvent interactions and that explicit treatment of solvent, such as EFP, is essential for achieving quantitative accuracy.« less

Selectivity in reversed-phase separations: general influence of solvent type and mobile phase pH.

PubMed

Neue, Uwe D; Méndez, Alberto

2007-05-01

The influence of the mobile phase on retention is studied in this paper for a group of over 70 compounds with a broad range of multiple functional groups. We varied the pH of the mobile phase (pH 3, 7, and 10) and the organic modifier (methanol, acetonitrile (ACN), and tetrahydrofuran (THF)), using 15 different stationary phases. In this paper, we describe the overall retention and selectivity changes observed with these variables. We focus on the primary effects of solvent choice and pH. For example, transfer rules for solvent composition resulting in equivalent retention depend on the packing as well as on the type of analyte. Based on the retention patterns, one can calculate selectivity difference values for different variables. The selectivity difference is a measure of the importance of the different variables involved in method development. Selectivity changes specific to the type of analyte are described. The largest selectivity differences are obtained with pH changes.

Attenuation of Multiple Organ Damage by Continuous Low-Dose Solvent-Free Infusions of Resveratrol after Severe Hemorrhagic Shock in Rats

PubMed Central

Kirsch, Michael; Petrat, Frank

2017-01-01

Therapeutic effects of continuous intravenous infusions of solvent-free low doses of resveratrol on organ injury and systemic consequences resulting from severe hemorrhagic shock in rats were studied. Hemorrhagic shock was induced by withdrawing arterial blood until a mean arterial blood pressure (MAP) of 25–30 mmHg was reached. Following a shock phase of 60 min, rats were resuscitated with the withdrawn blood plus lactated Ringer’s. Resveratrol (20 or 60 μg/kg × h) was continuously infused intravenously starting with the resuscitation phase (30 min) and continued until the end of the experiment (total treatment time 180 min). Animals of the shock control group received 0.9% NaCl solution. After the observation phase (150 min), rats were sacrificed. Resveratrol significantly stabilized the MAP and peripheral oxygen saturation after hemorrhagic shock, decreased the macroscopic injury of the small intestine, significantly attenuated the shock-induced increase in tissue myeloperoxidase activity in the small intestine, liver, kidney and lung, and diminished tissue hemorrhages (particularly in the small intestine and liver) as well as the rate of hemolysis. Already very low doses of resveratrol, continuously infused during resuscitation after severe hemorrhagic shock, can significantly improve impaired systemic parameters and attenuate multiple organ damage in rats. PMID:28817064

Comparison of spray drying, electroblowing and electrospinning for preparation of Eudragit E and itraconazole solid dispersions.

PubMed

Sóti, Péter Lajos; Bocz, Katalin; Pataki, Hajnalka; Eke, Zsuzsanna; Farkas, Attila; Verreck, Geert; Kiss, Éva; Fekete, Pál; Vigh, Tamás; Wagner, István; Nagy, Zsombor K; Marosi, György

2015-10-15

Three solvent based methods: spray drying (SD), electrospinning (ES) and air-assisted electrospinning (electroblowing; EB) were used to prepare solid dispersions of itraconazole and Eudragit E. Samples with the same API/polymer ratios were prepared in order to make the three technologies comparable. The structure and morphology of solid dispersions were identified by scanning electron microscopy and solid phase analytical methods such as, X-ray powder diffraction (XRPD), differential scanning calorimetry (DSC) and Raman chemical mapping. Moreover, the residual organic solvents of the solid products were determined by static headspace-gas chromatography/mass spectroscopy measurements and the wettability of samples was characterized by contact angle measurement. The pharmaceutical performance of the three dispersion type, evaluated by dissolution tests, proved to be very similar. According to XRPD and DSC analyses, made after the production, all the solid dispersions were free of any API crystal clusters but about 10 wt% drug crystallinity was observed after three months of storage in the case of the SD samples in contrast to the samples produced by ES and EB in which the polymer matrix preserved the API in amorphous state. Copyright © 2015 Elsevier B.V. All rights reserved.

Electric field-driven, magnetically-stabilized ferro-emulsion phase contactor

DOEpatents

Scott, T.C.

1990-07-17

Methods and systems are disclosed for interfacial surface area contact between a dispersed phase liquid and a continuous phase liquid in counter-current flow for purposes such as solvent extraction. Initial droplets of a dispersed phase liquid material containing ferromagnetic particles functioning as a packing'' are introduced to a counter-current flow of the continuous phase. A high intensity pulsed electric field is applied so as to shatter the initial droplets into a ferromagnetic emulsion comprising many smaller daughter droplets having a greater combined total surface area than that of the initial droplets in contact with the continuous phase material. A magnetic field is applied to control the position of the ferromagnetic emulsion for enhanced coalescence of the daughter droplets into larger reformed droplets. 2 figs.

Electric field-driven, magnetically-stabilized ferro-emulsion phase contactor

DOEpatents

Scott, Timothy C.

1990-01-01

Methods and systems for interfacial surface area contact between a dispersed phase liquid and a continuous phase liquid in counter-current flow for purposes such as solvent extraction. Initial droplets of a dispersed phase liquid material containing ferromagnetic particles functioning as a "packing" are introduced to a counter-current flow of the continuous phase. A high intensity pulsed electric field is applied so as to shatter the initial droplets into a ferromagnetic emulsion comprising many smaller daughter droplets having a greater combined total surface area than that of the initial droplets in contact with the continuous phase material. A magnetic field is applied to control the position of the ferromagnetic emulsion for enhanced coalescence of the daughter droplets into larger reformed droplets.

Micro versus macro solid phase extraction for monitoring water contaminants: a preliminary study using trihalomethanes.

PubMed

Alexandrou, Lydon D; Spencer, Michelle J S; Morrison, Paul D; Meehan, Barry J; Jones, Oliver A H

2015-04-15

Solid phase extraction is one of the most commonly used pre-concentration and cleanup steps in environmental science. However, traditional methods need electrically powered pumps, can use large volumes of solvent (if multiple samples are run), and require several hours to filter a sample. Additionally, if the cartridge is open to the air volatile compounds may be lost and sample integrity compromised. In contrast, micro cartridge based solid phase extraction can be completed in less than 2 min by hand, uses only microlitres of solvent and provides comparable concentration factors to established methods. It is also an enclosed system so volatile components are not lost. The sample can also be eluted directly into a detector (e.g. a mass spectrometer) if required. However, the technology is new and has not been much used for environmental analysis. In this study we compare traditional (macro) and the new micro solid phase extraction for the analysis of four common volatile trihalomethanes (trichloromethane, bromodichloromethane, dibromochloromethane and tribromomethane). The results demonstrate that micro solid phase extraction is faster and cheaper than traditional methods with similar recovery rates for the target compounds. This method shows potential for further development in a range of applications. Copyright © 2015 Elsevier B.V. All rights reserved.

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

PubMed

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

2017-07-21

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

Carbon nanotube (CNT) and nanofibrillated cellulose (NFC) reinforcement effect on thermoplastic polyurethane (TPU) scaffolds fabricated via phase separation using dimethyl sulfoxide (DMSO) as solvent.

PubMed

Mi, Hao-Yang; Jing, Xin; Salick, Max R; Cordie, Travis M; Turng, Lih-Sheng

2016-09-01

Although phase separation is a simple method of preparing tissue engineering scaffolds, it suffers from organic solvent residual in the scaffold. Searching for nontoxic solvents and developing effective solvent removal methods are current challenges in scaffold fabrication. In this study, thermoplastic polyurethane (TPU) scaffolds containing carbon nanotubes (CNTs) or nanofibrillated cellulose fibers (NFCs) were prepared using low toxicity dimethyl sulfoxide (DMSO) as a solvent. The effects of two solvent removal approaches on the final scaffold morphology were studied. The freeze drying method caused large pores, with small pores on the pore walls, which created connections between the pores. Meanwhile, the leaching and freeze drying method led to interconnected fine pores with smaller pore diameters. The nucleation effect of CNTs and the phase separation behavior of NFCs in the TPU solution resulted in significant differences in the microstructures of the resulting scaffolds. The mechanical performance of the nanocomposite scaffolds with different morphologies was investigated. Generally, the scaffolds with a fine pore structure showed higher compressive properties, and both the CNTs and NFCs improved the compressive properties of the scaffolds, with greater enhancement found in TPU/NFC nanocomposite scaffolds. In addition, all scaffolds showed good sustainability under cyclical load bearing, and the biocompatibility of the scaffolds was verified via 3T3 fibroblast cell culture. Copyright © 2016 Elsevier Ltd. All rights reserved.

Liquid-liquid equilibria for the ternary systems sulfolane + octane + benzene, sulfolane + octane + toluene and sulfolane + octane + p-xylene

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

Lee, S.; Kim, H.

1995-03-01

Sulfolane is widely used as a solvent for the extraction of aromatic hydrocarbons. Ternary phase equilibrium data are essential for the proper understanding of the solvent extraction process. Liquid-liquid equilibrium data for the systems sulfolane + octane + benzene, sulfolane + octane + toluene and sulfolane + octane + p-xylene were determined at 298.15, 308.15, and 318.15 K. Tie line data were satisfactorily correlated by the Othmer and Tobias method. The experimental data were compared with the values calculated by the UNIQUAC and NRTL models. Good quantitative agreement was obtained with these models. However, the calculated values based on themore » NRTL model were found to be better than those based on the UNIQUAC model.« less

Development of an impact- and solvent-resistant thermoplastic composite matrix, phase 4

NASA Technical Reports Server (NTRS)

Delano, C. B.

1987-01-01

Polyimides from BTDA with m-phenylenediamine and three aliphatic diamines were prepared in cresol and characterized. Characterization tests included compression strength and modulus, stressed solvent resistance, and melt-flow tests. Efforts to reduce the molecular weights of these polymers by either stoichiometric imbalance or phthalic anhydride end capping produced opacity in the polymer moldings when the stoichiometry was less than 99 percent. Use of 2,4-diaminotoluene in place of the m-phenylenediamine allowed clear polymer moldings to be obtained at all stoichiometries by end capping or stoichiometric imbalance. After melt-flow/molecular-weight studies, carbon fabric composites were prepared from three polyimide compositions containing BTDA, 2,4-diaminotoluene and two aliphatic diamines. Flexural strengths of two of the resins were in excess of 689 MPa (100 ksi) at both room temperature and 93 C. The polyimide from BTDA was selected for scale-up and neat resin characterization tests. The Tg of this polymer was 233 C.

Reversible Interconversion between 2,5-Dimethylpyrazine and 2,5-Dimethylpiperazine by Iridium-Catalyzed Hydrogenation/Dehydrogenation for Efficient Hydrogen Storage.

PubMed

Fujita, Ken-Ichi; Wada, Tomokatsu; Shiraishi, Takumi

2017-08-28

A new hydrogen storage system based on the hydrogenation and dehydrogenation of nitrogen heterocyclic compounds, employing a single iridium catalyst, has been developed. Efficient hydrogen storage using relatively small amounts of solvent compared with previous systems was achieved by this new system. Reversible transformations between 2,5-dimethylpyrazine and 2,5-dimethylpiperazine, accompanied by the uptake and release of three equivalents of hydrogen, could be repeated almost quantitatively at least four times without any loss of efficiency. Furthermore, hydrogen storage under solvent-free conditions was also accomplished. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

An ammonium sulfate/ethanol aqueous two-phase system combined with ultrasonication for the separation and purification of lithospermic acid B from Salvia miltiorrhiza Bunge.

PubMed

Guo, Y X; Han, J; Zhang, D Y; Wang, L H; Zhou, L L

2012-07-01

We studied the effect of ultrasonication extraction technology combined with ammonium sulfate/ethanol aqueous two-phase system (ATPS) for the separation of lithospermic acid B (LAB) from Salvia miltiorrhiza Bunge. According to the literature and preliminary studies, ammonium sulfate concentration, ethanol concentration, pH, ultrasonication power, ultrasonication time and the ratio of solvent-to-solid were investigated using a single factor design to identify the factors affecting separation. Taking into consideration a simultaneous increase in LAB recovery (R (%)) and partition coefficient (K), the best performance of the ATPS was obtained at 25°C and pH 2 using ammonium sulfate 22% (w/w) and ethanol 30% (w/w). To keep the solvent-to-solid ratio at 10, response surface methodology was used to find the optimal ultrasonication power and ultrasonication time. Quadratic models were predicted for LAB yield in the upper phase. Optimal conditions of 572.1 W ultrasonication power and 42.2 min produced a maximum yield of LAB of 42.16 mg g(-1) sample. There was no obvious degradation of LAB with ultrasound under the applied conditions, and the experimental yield of LAB was 42.49 mg g(-1) sample and the purity was 55.28% (w/w), which was much higher than that obtained using conventional extraction. The present study demonstrated that ultrasound coupled with aqueous two-phase systems is very efficient tool for the extraction and purification of LAB from Salvia miltiorrhiza Bunge. Copyright © 2011 Elsevier B.V. All rights reserved.

Focused microwave-assisted solvent extraction and HPLC determination of effective constituents in Eucommia ulmodies Oliv. (E. ulmodies).

PubMed

Li, Hui; Chen, Bo; Zhang, Zhaohui; Yao, Shouzhuo

2004-06-17

A new focused microwave-assisted solvent extraction method using water as solvent has been developed for leaching geniposidic and chlorogenic acids from Eucommia ulmodies Oliv. The extraction procedures were optimized using a two indexes orthogonal experimental design and graphical analysis, by varying irradiation time, solvent volume, solvent composition and microwave power. The optimum extraction conditions were obtained: for geniposidic acid, 50% micorwave power, 40s irradiation, and 80% (v/v) aqueous methanol as extraction solvent (20mlg(-1) sample); and for chlorogenic acid, 50% micorwave power, 30s irradiation, and 20% aqueous methanol (20mlg(-1) sample). The composition of the extraction solvent was optimized and can be directly used as the mobile phase in the HPLC separation. Quantification of organic acids was done by HPLC at room temperature using Spherigel C(18) chromatographic column (250 mm x4.6 mm , i.d. 5mum), the methanol:water:acetic acid (20:80:1.0, v/v) mobile phase and UV detection at 240nm. The R.S.D. of the extraction process for geniposidic and chlorogenic acid were 3.8 and 4.1%, respectively.

Attractive design: an elution solvent optimization platform for magnetic-bead-based fractionation using digital microfluidics and design of experiments.

PubMed

Lafrenière, Nelson M; Mudrik, Jared M; Ng, Alphonsus H C; Seale, Brendon; Spooner, Neil; Wheeler, Aaron R

2015-04-07

There is great interest in the development of integrated tools allowing for miniaturized sample processing, including solid phase extraction (SPE). We introduce a new format for microfluidic SPE relying on C18-functionalized magnetic beads that can be manipulated in droplets in a digital microfluidic platform. This format provides the opportunity to tune the amount (and potentially the type) of stationary phase on-the-fly, and allows the removal of beads after the extraction (to enable other operations in same device-space), maintaining device reconfigurability. Using the new method, we employed a design of experiments (DOE) operation to enable automated on-chip optimization of elution solvent composition for reversed phase SPE of a model system. Further, conditions were selected to enable on-chip fractionation of multiple analytes. Finally, the method was demonstrated to be useful for online cleanup of extracts from dried blood spot (DBS) samples. We anticipate this combination of features will prove useful for separating a wide range of analytes, from small molecules to peptides, from complex matrices.

Matrix solid-phase dispersion technique for the determination of a new antiallergic drug, bilastine, in rat faeces.

PubMed

Berrueta, L A; Fernández-Armentia, M; Bakkali, A; Gonzalo, A; Lucero, M L; Orjales, A

2001-08-25

A matrix solid-phase dispersion (MSPD) procedure for the isolation and HPLC determination of a new antiallergic agent, bilastine, in rat faeces is presented. The effect on recovery of empirical variables such as nature, pH and volume of the washing and elution liquids and nature of the adsorbent has been tested. The best recoveries were attained using an octadecylsilyl sorbent, 10 ml of a 0.1 M NaHCO3-Na2CO3 aqueous buffer of pH 10.0 as washing solvent and 10 ml of methanol as elution solvent. The extracts were evaporated to dryness and reconstituted in mobile phase before their injection into a HPLC system, equipped with a Discovery RP-amide C16 column and a fluorescence detector. The method allows one to reach recoveries of 95.0% within the concentration range 0.05-10 microg/g, with within-day repeatabilities of less than 5% and between-day repeatabilities of less than 9% within this range. This method has been successfully applied to the excretion studies of bilastine in the rat.

Steroid biotransformations in biphasic systems with Yarrowia lipolytica expressing human liver cytochrome P450 genes

PubMed Central

2012-01-01

Background Yarrowia lipolytica efficiently metabolizes and assimilates hydrophobic compounds such as n-alkanes and fatty acids. Efficient substrate uptake is enabled by naturally secreted emulsifiers and a modified cell surface hydrophobicity and protrusions formed by this yeast. We were examining the potential of recombinant Y. lipolytica as a biocatalyst for the oxidation of hardly soluble hydrophobic steroids. Furthermore, two-liquid biphasic culture systems were evaluated to increase substrate availability. While cells, together with water soluble nutrients, are maintained in the aqueous phase, substrates and most of the products are contained in a second water-immiscible organic solvent phase. Results For the first time we have co-expressed the human cytochromes P450 2D6 and 3A4 genes in Y. lipolytica together with human cytochrome P450 reductase (hCPR) or Y. lipolytica cytochrome P450 reductase (YlCPR). These whole-cell biocatalysts were used for the conversion of poorly soluble steroids in biphasic systems. Employing a biphasic system with the organic solvent and Y. lipolytica carbon source ethyl oleate for the whole-cell bioconversion of progesterone, the initial specific hydroxylation rate in a 1.5 L stirred tank bioreactor was further increased 2-fold. Furthermore, the product formation was significantly prolonged as compared to the aqueous system. Co-expression of the human CPR gene led to a 4-10-fold higher specific activity, compared to the co-overexpression of the native Y. lipolytica CPR gene. Multicopy transformants showed a 50-70-fold increase of activity as compared to single copy strains. Conclusions Alkane-assimilating yeast Y. lipolytica, coupled with the described expression strategies, demonstrated its high potential for biotransformations of hydrophobic substrates in two-liquid biphasic systems. Especially organic solvents which can be efficiently taken up and/or metabolized by the cell might enable more efficient bioconversion as compared to aqueous systems and even enable simple, continuous or at least high yield long time processes. PMID:22876969

In-syringe demulsified dispersive liquid-liquid microextraction and high performance liquid chromatography-mass spectrometry for the determination of trace fungicides in environmental water samples.

PubMed

Xia, Yating; Cheng, Min; Guo, Feng; Wang, Xiangfang; Cheng, Jing

2012-04-29

An in-syringe demulsified dispersive liquid-liquid microextraction (ISD-DLLME) technique was developed using low-density extraction solvents for the highly sensitive determination of the three trace fungicides (azoxystrobin, diethofencarb and pyrimethanil) in water samples by high performance liquid chromatography-mass spectrometry chromatography-diode array detector/electrospray ionisation mass spectrometry. In the proposed technique, a 5-mL syringe was used as an extraction, separation and preconcentration container. The emulsion was obtained after the mixture of toluene (extraction solvent) and methanol (dispersive solvent) was injected into the aqueous bulk of the syringe. The obtained emulsion cleared into two phases without centrifugation, when an aliquot of methanol was introduced as a demulsifier. The separated floating organic extraction solvent was impelled and collected into a pipette tip fitted to the tip of the syringe. Under the optimal conditions, the enrichment factors for azoxystrobin, diethofencarb and pyrimethanil were 239, 200, 195, respectively. The limits of detection, calculated as three times the signal-to-noise ratio (SN(-1)), were 0.026 μg L(-1) for azoxystrobin, 0.071 μg L(-1) for diethofencarb and 0.040 μg L(-1) for pyrimethanil. The repeatability study was carried out by extracting the spiked water samples at concentration levels of 0.02 μg mL(-1) for all the three fungicides. The relative standard deviations varied between 4.9 and 8.2% (n=5). The recoveries of all the three fungicides from tap, lake and rain water samples at spiking levels of 0.2, 1, 5 μg L(-1) were in the range of 90.0-105.0%, 86.0-114.0% and 88.6-110.0%, respectively. The proposed ISD-DLLME technique was demonstrated to be simple, practical and efficient for the determination of different kinds of fungicide residues in real water samples. Copyright © 2012. Published by Elsevier B.V.

Simultaneous determination of inorganic anions and cations by supercritical fluid chromatography using evaporative light scattering detection.

PubMed

Foulon, Catherine; Di Giulio, Pauline; Lecoeur, Marie

2018-01-26

Supercritical fluid chromatography (SFC) is commonly used for the analysis of non-polar compounds, but remains poorly explored for the separation of polar and ionized molecules. In this paper, SFC has been investigated for the separation of 14 inorganic ions sampled in aqueous solutions. Four polar stationary phases were first screened using CO 2 -methanol-based mobile phases containing water or different acidic or basic additives, in order to select the most efficient conditions for the simultaneous retention of inorganic cations and anions and to favor their detection using evaporative light scattering detector (ELSD). Orthogonal selectivity was obtained depending on the stationary phase used: whereas anions are less retained on HILIC stationary phase, 2-ethylpyridine (2-EP) stationary phase exhibits strong interaction for anions. Best results were obtained under gradient elution mode using a 2-EP stationary phase and by adding 0.2% triethylamine in the CO 2 -methanol-based mobile phase. The composition of the injection solvent was also investigated. The results showed that a methanolic sample containing a percentage of water not exceeding 20% does not affect the analytical performances obtained on 2-EP. Moreover, the presence of triethylamine in the injection solvent contributes to eliminate peaks shoulders. Among the 14 inorganic ions tested, three cations (Li + , Ca 2+ and Mg 2+ ) and five anions (Cl - , Br - , NO 3 - , I - , SCN - ) were totally resolved in 15 min. NO 3 - and NO 2 - still coeluted in the final optimized conditions. The other investigated ions were either strongly retained on the stationary phase or not detected by the ELSD. Copyright © 2017 Elsevier B.V. All rights reserved.

Surface Nanobubbles in Nonaqueous Media: Looking for Nanobubbles in DMSO, Formamide, Propylene Carbonate, Ethylammonium Nitrate, and Propylammonium Nitrate.

PubMed

An, Hongjie; Liu, Guangming; Atkin, Rob; Craig, Vincent S J

2015-07-28

Surface nanobubbles produced by supersaturation during the exchange of ethanol for water are routinely observed on hydrophobic surfaces, are stable for days, and have contact angles that are very much greater than observed macroscopically. Here, we test the hypothesis that nanobubbles can also be observed in nonaqueous solvents in order to ascertain if their anomalous lifetimes and contact angles are related to properties of the solvent. Nanobubbles were seen in the protic solvents formamide, ethylammonium nitrate, and propylammonium nitrate, but not in propylene carbonate or dimethyl sulfoxide. Solvents in which nanobubbles were observed exhibit a three-dimensional hydrogen-bonding network. Like in aqueous systems, the nanobubbles were stable for days and exhibited high contact angles (∼165°).

Preparation of hemoglobin-loaded nano-sized particles with porous structure as oxygen carriers.

PubMed

Zhao, Jian; Liu, Chang-Sheng; Yuan, Yuan; Tao, Xin-Yi; Shan, Xiao-Qian; Sheng, Yan; Wu, Fan

2007-03-01

Hb (hemoglobin)-loaded particles (HbP) encapsulated by a biodegradable polymer used as oxygen carrier were prepared. A modified double emulsion and solvent diffusion/evaporation method was adopted. All experiments were performed based on two types of biodegradable polymers, poly(epsilon-caprolactone) (PCL) and poly(epsilon-caprolactone-ethylene glycol) (PCL-PEG). The biodistribution and the survival time in blood of the particles were investigated in a mouse model. Encapsulation efficiency and pore-connecting efficiency were evaluated by a novel sulfocyanate potassium method. The influence of process parameters on the particle size and pore-connecting efficiency (PCE%) of nanoparticles have been discussed. The prepared conditions: solvent, external aqueous phase, pressure were discussed. The system utilizing dichloromethane (DCM)/ethyl acetate (EA) as a solvent with an unsaturated external aqueous phase yielded the highest encapsulation efficiency (87.35%) with a small mean particle size (153 nm). The formation of porous channels was attributed to the diffusion of solvent. The PCE% was more sensitive to the rate of solvent diffusion that was obviously affected by the preparation temperature. The PCE% reached 87.47% when PCL-PEG was employed at 25 degrees C. P(50) of HbP was 27 mmHg, which does not seem to be greatly affected by the encapsulation procedure. In vivo, following intravenous injection of 6-coumarin labeled HbP, the major organ accumulating Hb-loaded particles was the liver. The half-life of nano-sized PCL HbP was 3.1 times as long as the micro-sized PCL HbP. Also, Nano-sized as well as a PEGylated surface on HbP is beneficial for prolonged blood residence (7.2 fold increase).

Induced amphotropic and thermotropic ionic liquid crystallinity in phosphonium halides: "lubrication" by hydroxyl groups.

PubMed

Ma, Kefeng; Somashekhar, B S; Gowda, G A Nagana; Khetrapal, C L; Weiss, Richard G

2008-03-18

The influence of covalently attaching hydroxymethylene to the methyl groups of methyl-tri-n-alkylphosphonium halides (where the alkyl chains are decyl, tetradecyl, or octadecyl and the halide is chloride or bromide) or adding methanol as a solute to the salts on their solid, liquid-crystalline (smectic A2), and isotropic phases has been investigated using a variety of experimental techniques. These structural and compositional changes are found to induce liquid crystallinity in some cases and to enhance the temperature range and lower the onset temperature of the liquid-crystalline phases in some others. The results are interpreted in terms of the lengths of the three n-alkyl chains attached to the phosphorus cation, the nature of the halide anion, the influence of H-bonding interactions at the head group regions of the layered phases, and other solvent-solute interactions. The fact that at least 1 molar equiv of methanol must be added to effect complete (isothermal) conversion of a solid methyl-tri-n-alkylphosphonium salt to a liquid crystal demonstrates a direct and strong association between individual methanol molecules and the phosphonium salts. Possible applications of such systems are suggested.

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

PubMed

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

2016-12-01

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

Binary nanoparticle superlattices of soft-particle systems

DOE PAGES

Travesset, Alex

2015-08-04

The solid-phase diagram of binary systems consisting of particles of diameter σ A=σ and σ B=γσ (γ≤1) interacting with an inverse p = 12 power law is investigated as a paradigm of a soft potential. In addition to the diameter ratio γ that characterizes hard-sphere models, the phase diagram is a function of an additional parameter that controls the relative interaction strength between the different particle types. Phase diagrams are determined from extremes of thermodynamic functions by considering 15 candidate lattices. In general, it is shown that the phase diagram of a soft repulsive potential leads to the morphological diversitymore » observed in experiments with binary nanoparticles, thus providing a general framework to understand their phase diagrams. In addition, particular emphasis is shown to the two most successful crystallization strategies so far: evaporation of solvent from nanoparticles with grafted hydrocarbon ligands and DNA programmable self-assembly.« less

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

Droplet microfluidics with a nanoemulsion continuous phase.

PubMed

Gu, Tonghan; Yeap, Eunice W Q; Somasundar, Ambika; Chen, Ran; Hatton, T Alan; Khan, Saif A

2016-07-05

We present the first study of a novel, generalizable method that uses a water-in-oil nanoemulsion as the continuous phase to generate uniform aqueous micro-droplets in a capillary-based microfluidic system. We first study the droplet generation mechanism in this system and compare it to the more conventional case where a simple oil/solvent (with surfactant) is used as the continuous phase. Next, we present two versatile methods - adding demulsifying chemicals and heat treatment - to allow active online chemical interaction between the continuous and dispersed phases. These methods allow each generated micro-droplet to act as a well-mixed micro-reactor with walls that are 'permeable' to the nanoemulsion droplets and their contents. Finally, we demonstrate an application of this system in the fabrication of uniform hydrogel (alginate) micro-beads with control over particle properties such as size and swelling. Our work expands the toolbox of droplet-based microfluidics, enabling new opportunities and applications involving active colloidal continuous phases carrying chemical payloads, both in advanced materials synthesis and droplet-based screening and diagnostic methods.

Application of finite inverse gas chromatography in hypromellose acetate succinate-water-acetone systems.

PubMed

Chiu, Sheng-Wei; Sturm, Derek R; Moser, Justin D; Danner, Ronald P

2016-09-30

A modification of a GC was developed to investigate both infinitely dilute and finite concentrations of solvents in polymers. Thermodynamic properties of hypromellose acetate succinate (HPMCAS-L)-acetone-water systems are important for the optimization of spray-drying processes used in pharmaceutical manufacturing of solid dispersion formulations. These properties, at temperatures below the glass transition temperature, were investigated using capillary column inverse gas chromatography (CCIGC). Water was much less soluble in the HPMCAS-L than acetone. Experiments were also conducted at infinitely dilute concentrations of one of the solvents in HPMCAS-L that was already saturated with the other solvent. Overall the partitioning of the water was not significantly affected by the presence of either water or acetone in the polymer. The acetone partition coefficient decreased as either acetone or water was added to the HPMCAS-L. A representation of the HPMCAS-L structure in terms of UNIFAC groups has been developed. With these groups, the UNIFAC-vdw-FV model did a reasonable job of predicting the phase equilibria in the binary and ternary systems. The Flory-Huggins correlation with fitted interaction parameters represented the data well. Copyright © 2016 Elsevier B.V. All rights reserved.

Solvent coarsening around colloids driven by temperature gradients

NASA Astrophysics Data System (ADS)

Roy, Sutapa; Dietrich, Siegfried; Maciolek, Anna

2018-04-01

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

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

DOEpatents

Arnold, Jr., Wesley D.

1977-01-01

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

Preparative separation of two subsidiary colors of FD&C Yellow No. 5 (Tartrazine) using spiral high-speed counter-current chromatography◊

PubMed Central

Roque, Jose A.; Mazzola, Eugene P.; Ito, Yoichiro

2014-01-01

Specifications in the U.S. Code of Federal Regulations for the color additive FD&C Yellow No. 5 (Colour Index No. 19140) limit the level of the tetrasodium salt of 4-[(4',5-disulfo[1,1'-biphenyl]-2-yl)hydrazono]-4,5-dihydro-5-oxo-1-(4-sulfophenyl)-1H-pyrazole-3-carboxylic acid and that of the trisodium salt of 4,4'-[4,5-dihydro-5-oxo-4-[(4-sulfophenyl)hydrazono]-1H-pyrazol-1,3-diyl]bis[benzenesulfonic acid], which are subsidiary colors abbreviated as Pk5 and Pk7, respectively. Small amounts of Pk5 and Pk7 are needed by the U.S. Food and Drug Administration for confirmatory analyses and for development of analytical methods. The present study describes the use of spiral high-speed counter-current chromatography (HSCCC) with the recently introduced highly polar organic/high-ionic strength aqueous solvent systems to separate Pk5 and Pk7 from a sample of FD&C Yellow No. 5 containing ~3.5% Pk5 and ~0.7% Pk7. Multiple ~1.0 g portions of FD&C Yellow No. 5 (totaling 6.4 g dye) were separated, using the upper phase of the solvent system 1-BuOH/EtOHabs/saturated ammonium sulfate/water, 1.7:0.3:1:1, v/v/v/v, as the mobile phase. After applying a specially developed method for removing the ammonium sulfate from the HSCCC-collected fractions, these separations resulted in an enriched mixture (~160 mg) of Pk5 and Pk7 (~46% and ~21%, respectively). Separation of the enriched mixture, this time using the lower phase of that solvent system as the mobile phase, resulted in ~ 61 mg of Pk5 collected in fractions whose purity ranged from 88.0% to 92.7% (by HPLC at 254 nm). Pk7 (20.7 mg, ~83% purity) was recovered from the upper phase of the column content. Application of this procedure also resulted in purifying the major component of FD&C Yellow No. 5 to >99% purity. The separated compounds were characterized by high-resolution mass spectrometry and several 1H and 13C nuclear magnetic resonance spectroscopic techniques (COSY, NOESY, HSQC, and HMBC). PMID:24755184

Dynamics of the solute-solvent interactions of electronically excited 4-N,N-dimethylaminobenzonitrile (DMABN) and of 3,5,N,N-tetramethyl-4-aminobenzonitrile (TMABN) dissolved in viscous alcohols and in a viscous nitrile

NASA Astrophysics Data System (ADS)

Weisenborn, Petra C. M.; Huizer, A. Herbert; Varma, Cyril A. G. O.

1989-06-01

The time dependence of the fluorescence of solutions of 4-N,N-dimethylaminobenzonitrile (DMABN) and 3,5,N,N-tetramethyl-4-aminobenzonitrile (TMA BN) in neat polar solvents has been investigated, using a 25 ps UV-laser pulse for excitation and a streak camera for detection. Both the compounds DMABN and TMABN exhibit normal fluorescence F N and anomalous fluorescence F A, but all the solutions of TMABN show merely a single band in the fluorescence spectrum, which is a superposition of the bands F N and F A. In the case of DMABN the fluorescence in the region λ < 400 nm, where F N dominates, the fluorescence decays tri-exponentially due to fluorescence from three types of species, namely excited solute-solvent complexes, excited bare solutes and solute-solvent exciplexes. Within the lifetime of these emitting species there is probably no reverse reaction from exciplexes to excited solute-solvent complexes or excited bare solutes. This is in contrast with a previously presented picture, which includes such a reverse reaction. In the case of the solution of DMABN in n-butanol, the fluorescence at λ < 400 nm is bi-exponential. We show that this is due to an accidental degeneracy of two lifetimes. In contrast to a previous conclusion, we find that DMABN exists partially in the form of ground state solute-solvent complexes also in the solution in nitriles. The anomalous fluorescence develops in two phases, in the first one solute-solvent exciplexes are formed and in the second one the dielectric polarization of the solvent around the exciplex builds up. The rate constant for the formation of the anomalously fluorescing species, i.e. solute-solvent exciplexes, bears no relation with the longitudinal relaxation time, as claimed to have been shown previously.

Polytetrafluorethylene film-based liquid-three phase micro extraction coupled with differential pulse voltammetry for the determination of atorvastatin calcium.

PubMed

Ensafi, Ali A; Khoddami, Elaheh; Rezaei, Behzad

2013-01-01

In this paper, we describe a new combination method based on polytetrafluorethylene (PTFE) film-based liquid three-phase micro extraction coupled with differential pulse voltammetry (DPV) for the micro extraction and quantification of atorvastatin calcium (ATC) at the ultra-trace level. Different factors affecting the liquid-three phases micro extraction of atorvastatin calcium, including organic solvent, pH of the donor and acceptor phases, concentration of salt, extraction time, stirring rate and electrochemical factors, were investigated, and the optimal extraction conditions were established. The final stable signal was achieved after a 50 min extraction time, which was used for analytical applications. An enrichment factor of 21 was achieved, and the relative standard deviation (RSD) of the method was 4.5% (n = 4). Differential pulse voltammetry exhibited two wide linear dynamic ranges of 20.0-1000.0 pmol L(-1) and 0.001-11.0 µmol L(-1) of ATC. The detection limit was found to be 8.1 pmol L(-1) ATC. Finally, the proposed method was used as a new combination method for the determination of atorvastatin calcium in real samples, such as human urine and plasma.

Model forecasting of phase composition of electrolytic alloys Co-Ni-Mn (part 1)

NASA Astrophysics Data System (ADS)

Schmidt, V. V.; Zhikhareva, I. G.

2018-03-01

With the help of four criteria for phase formation, a model forecasting of the phase composition of electrolytic alloy Co-Ni-Mn was carried out; the expected phases were calculated. The boundaries of the chemical content of the metal-solvent (Co) in these phases are determined, depending on the ratio of metal ions in the electrolyte of deposition. Model forecasting of the phase composition of Co-Ni-Mn alloys makes it possible to predict the type and number of Co phases (hexagonal close-packed - HCP-α-Co, face-centered cubic - FCC-β-Co) depending on the mole fraction of the solvent metal (Co). In the first approximation, the forecast allows one to determine the phase and chemical composition of the coating, which corresponds to the specified operational properties.

Biosynthesis of glycerol carbonate from glycerol by lipase in dimethyl carbonate as the solvent.

PubMed

Lee, Kyung Hwa; Park, Chang-Ho; Lee, Eun Yeol

2010-11-01

Glycerol carbonate was synthesized from renewable glycerol and dimethyl carbonate using lipase in solvent-free reaction system in which excess dimethyl carbonate played as the reaction medium. A variety of lipases have been tested for their abilities to catalyze transesterification reaction, and Candida antartica lipase B and Novozyme 435 exhibited higher catalytic activities. The silica-coated glycerol with a 1:1 ratio was supplied to prevent two-phase formation between hydrophobic dimethyl carbonate and hydrophilic glycerol. Glycerol carbonate was successfully synthesized with more than 90% conversion from dimethyl carbonate and glycerol with a molar ratio of 10 using Novozyme 435-catalyzed transesterification at 70 °C. The Novozyme 435 [5% (w/w) and 20% (w/w)] and silica gel were more than four times recycled with good stability in a repeated batch operation for the solvent-free synthesis of glycerol carbonate.

Unique Crystallization of Fullerenes: Fullerene Flowers

PubMed Central

Kim, Jungah; Park, Chibeom; Song, Intek; Lee, Minkyung; Kim, Hyungki; Choi, Hee Cheul

2016-01-01

Solution-phase crystallization of fullerene molecules strongly depends on the types of solvent and their ratios because solvent molecules are easily included in the crystal lattice and distort its structure. The C70 (solute)–mesitylene (solvent) system yields crystals with various morphologies and structures, such as cubes, tubes, and imperfect rods. Herein, using C60 and C70 dissolved in mesitylene, we present a novel way to grow unique flower-shaped crystals with six symmetric petals. The different solubility of C60 and C70 in mesitylene promotes nucleation of C70 with sixfold symmetry in the early stage, which is followed by co-crystallization of both C60 and C70 molecules, leading to lateral petal growth. Based on the growth mechanism, we obtained more complex fullerene crystals, such as multi-deck flowers and tube-flower complexes, by changing the sequence and parameters of crystallization. PMID:27561446

Ultrasonic-assisted continuous methanolysis of Jatropha curcas oil in the appearance of biodiesel used as an intermediate solvent.

PubMed

Kumar, Gajendra; Singh, Vidhi; Kumar, Dharmendra

2017-11-01

A environmental friendly system for fast transesterification of Jatropha curcas oil was developed for the production of biodiesel using an ultrasonic-assisted continuous tank reactor in the presence of fatty acid methyl ester (FAMEs) used as a green (intermediate) solvent with potassium hydroxide used as a catalyst. This research provide a new biodiesel production process, the optimal condition for the reaction were established: reaction temperature 25°C oil to methanol molar ratio was 1:5, catalyst concentration 0.75wt% of oil, solvent concentration 7.5%, flow rate 241.68±0.80ml/min, ultrasonic amplitude 60% and ultrasonic cycles 0.7s, transesterification was completed within 1.09min (residence time). The purity and conversion of biodiesel was 98.75±0.50% analyzed by the reverse phase HPLC method. Copyright © 2017 Elsevier B.V. All rights reserved.

Microalgae fractionation using steam explosion, dynamic and tangential cross-flow membrane filtration.

PubMed

Lorente, E; Hapońska, M; Clavero, E; Torras, C; Salvadó, J

2017-08-01

In this study, the microalga Nannochloropsis gaditana was subjected to acid catalysed steam explosion treatment and the resulting exploded material was subsequently fractionated to separate the different fractions (lipids, sugars and solids). Conventional and vibrational membrane setups were used with several polymeric commercial membranes. Two different routes were followed: 1) filtration+lipid solvent extraction and 2) lipid solvent extraction+filtration. Route 1 revealed to be much better since the used membrane for filtration was able to permeate the sugar aqueous phase and retained the fraction containing lipids; after this, an extraction required a much lower amount of solvent and a better recovering yield. Filtration allowed complete lipid rejection. Dynamic filtration improved permeability compared to the tangential cross-flow filtration. Best membrane performance was achieved using a 5000Da membrane with the dynamic system, obtaining a permeability of 6L/h/m 2 /bar. Copyright © 2017 Elsevier Ltd. All rights reserved.

Morphological Evolution of Gyroid-Forming Block Copolymer Thin Films with Varying Solvent Evaporation Rate.

PubMed

Wu, Yi-Hsiu; Lo, Ting-Ya; She, Ming-Shiuan; Ho, Rong-Ming

2015-08-05

In this study, we aim to examine the morphological evolution of block copolymer (BCP) nanostructured thin films through solvent evaporation at different rates for solvent swollen polystyrene-block-poly(l-lactide) (PS-PLLA). Interesting phase transitions from disorder to perpendicular cylinder and then gyroid can be found while using a partially selective solvent for PS to swell PS-PLLA thin film followed by solvent evaporation. During the transitions, gyroid-forming BCP thin film with characteristic crystallographic planes of (111)G, (110)G, and (211)G parallel to air surface can be observed, and will gradually transform into coexisting (110)G and (211)G planes, and finally transforms to (211)G plane due to the preferential segregation of constituted block to the surface (i.e., the thermodynamic origin for self-assembly) that affects the relative amount of each component at the air surface. With the decrease on the evaporation rate, the disorder phase will transform to parallel cylinder and then directly to (211)G without transition to perpendicular cylinder phase. Most importantly, the morphological evolution of PS-PLLA thin films is strongly dependent upon the solvent removal rate only in the initial stage of the evaporation process due to the anisotropy of cylinder structure. Once the morphology is transformed back to the isotropic gyroid structure after long evaporation, the morphological evolution will only relate to the variation of the surface composition. Similar phase transitions at the substrate can also be obtained by controlling the ratio of PLLA-OH to PS-OH homopolymers to functionalize the substrate. As a result, the fabrication of well-defined nanostructured thin films with controlled orientation can be achieved by simple swelling and deswelling with controlled evaporation rate.

Reliable Mechanochemistry: Protocols for Reproducible Outcomes of Neat and Liquid Assisted Ball-mill Grinding Experiments.

PubMed

Belenguer, Ana M; Lampronti, Giulio I; Sanders, Jeremy K M

2018-01-23

The equilibrium outcomes of ball mill grinding can dramatically change as a function of even tiny variations in the experimental conditions such as the presence of very small amounts of added solvent. To reproducibly and accurately capture this sensitivity, the experimentalist needs to carefully consider every single factor that can affect the ball mill grinding reaction under investigation, from ensuring the grinding jars are clean and dry before use, to accurately adding the stoichiometry of the starting materials, to validating that the delivery of solvent volume is accurate, to ensuring that the interaction between the solvent and the powder is well understood and, if necessary, a specific soaking time is added to the procedure. Preliminary kinetic studies are essential to determine the necessary milling time to achieve equilibrium. Only then can exquisite phase composition curves be obtained as a function of the solvent concentration under ball mill liquid assisted grinding (LAG). By using strict and careful procedures analogous to the ones here presented, such milling equilibrium curves can be obtained for virtually all milling systems. The system we use to demonstrate these procedures is a disulfide exchange reaction starting from the equimolar mixture of two homodimers to obtain at equilibrium quantitative heterodimer. The latter is formed by ball mill grinding as two different polymorphs, Form A and Form B. The ratio R = [Form B] / ([Form A] + [Form B]) at milling equilibrium depends on the nature and concentration of the solvent in the milling jar.