Trip report. Eurochemic company assistance: Hanford Atomic Products Operation spent fuel processing technology

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

Shank, E.M.

1959-06-23

Information obtained from HAPO during visit by M.K. Twichell, UCNC, and E.M. Shank, ORNL, is given. Included are the tentative procedures for obtaining and transmitting information to the Eurochemic company. Discussions are given on pulsed columns, corrosion, puse generators, centrifuges, valves, in-line instrumentation, evaporators, resin column design, off-gas processing, solvent recovery, liquid-waste handling, process control, equipment decontamination, criticality, radiation protection, diluent, and solvent stability, backmixing in a pulsed column, and use of 40% TBP in the purex flowsheet.

Identification of critical process variables affecting particle size following precipitation using a supercritical fluid.

PubMed

Sacha, Gregory A; Schmitt, William J; Nail, Steven L

2006-01-01

The critical processing parameters affecting average particle size, particle size distribution, yield, and level of residual carrier solvent using the supercritical anti-solvent method (SAS) were identified. Carbon dioxide was used as the supercritical fluid. Methylprednisolone acetate was used as the model solute in tetrahydrofuran. Parameters examined included pressure of the supercritical fluid, agitation rate, feed solution flow rate, impeller diameter, and nozzle design. Pressure was identified as the most important process parameter affecting average particle size, either through the effect of pressure on dispersion of the feed solution into the precipitation vessel or through the effect of pressure on solubility of drug in the CO2/organic solvent mixture. Agitation rate, impeller diameter, feed solution flow rate, and nozzle design had significant effects on particle size, which suggests that dispersion of the feed solution is important. Crimped HPLC tubing was the most effective method of introducing feed solution into the precipitation vessel, largely because it resulted in the least amount of clogging during the precipitation. Yields of 82% or greater were consistently produced and were not affected by the processing variables. Similarly, the level of residual solvent was independent of the processing variables and was present at 0.0002% wt/wt THF or less.

Self-assembly of nanocomposite materials

DOEpatents

Brinker, C. Jeffrey; Sellinger, Alan; Lu, Yunfeng

2001-01-01

A method of making a nanocomposite self-assembly is provided where at least one hydrophilic compound, at least one hydrophobic compound, and at least one amphiphilic surfactant are mixed in an aqueous solvent with the solvent subsequently evaporated to form a self-assembled liquid crystalline mesophase material. Upon polymerization of the hydrophilic and hydrophobic compounds, a robust nanocomposite self-assembled material is formed. Importantly, in the reaction mixture, the amphiphilic surfactant has an initial concentration below the critical micelle concentration to allow formation of the liquid-phase micellar mesophase material. A variety of nanocomposite structures can be formed, depending upon the solvent evaporazation process, including layered mesophases, tubular mesophases, and a hierarchical composite coating composed of an isotropic worm-like micellar overlayer bonded to an oriented, nanolaminated underlayer.

Quality of Chemical Safety Information in Printing Industry.

PubMed

Tsai, Chung-Jung; Mao, I-Fang; Ting, Jo-Yu; Young, Chi-Hsien; Lin, Jhih-Sian; Li, Wei-Lun

2016-04-01

Employees in printing industries can be exposed to multiple solvents in their work environment. The objectives of this study were to investigate the critical components of chemical solvents by analyzing the components of the solvents and collecting the Safety data sheets (SDSs), and to evaluate the hazard communication implementation status in printing industries. About 152 printing-related industries were recruited by area-stratified random sampling and included 23 plate-making, 102 printing and 27 printing-assistance companies in Taiwan. We analyzed company questionnaires (n = 152), SDSs (n = 180), and solvents (n = 20) collected from this sample of printing-related companies. Analytical results indicated that benzene and ethylbenzene, which were carcinogen and possibly carcinogen, were detectable in the cleaning solvents, and the detection rate were 54.5% (concentrations: <0.011-0.035 wt%) and 63.6% (concentrations: <0.011-6.22 wt%), respectively; however, neither compound was disclosed in the SDS for the solvents. Several other undisclosed components, including methanol, isopropanol and n-butanol, were also identified in the printing inks, fountain solutions and dilution solvents. We noted that, of the companies we surveyed, only 57.2% had a hazard communication program, 61.8% had SDSs on file and 59.9% provided employee safety and health training. We note that hazard communication programs were missing or ineffective in almost half of the 152 printing industries surveyed. Current safety information of solvents components in printing industries was inadequate, and many hazardous compounds were undisclosed in the SDSs of the solvents or the labels of the containers. The implementation of hazard communications in printing industries was still not enough for protecting the employees' safety and health. © The Author 2015. Published by Oxford University Press on behalf of the British Occupational Hygiene Society.

Quality of Chemical Safety Information in Printing Industry

PubMed Central

Tsai, Chung-Jung; Mao, I-Fang; Ting, Jo-Yu; Young, Chi-Hsien; Lin, Jhih-Sian; Li, Wei-Lun

2016-01-01

Objectives: Employees in printing industries can be exposed to multiple solvents in their work environment. The objectives of this study were to investigate the critical components of chemical solvents by analyzing the components of the solvents and collecting the Safety data sheets (SDSs), and to evaluate the hazard communication implementation status in printing industries. Method: About 152 printing-related industries were recruited by area-stratified random sampling and included 23 plate-making, 102 printing and 27 printing-assistance companies in Taiwan. We analyzed company questionnaires (n = 152), SDSs (n = 180), and solvents (n = 20) collected from this sample of printing-related companies. Results: Analytical results indicated that benzene and ethylbenzene, which were carcinogen and possibly carcinogen, were detectable in the cleaning solvents, and the detection rate were 54.5% (concentrations: <0.011–0.035 wt%) and 63.6% (concentrations: <0.011–6.22 wt%), respectively; however, neither compound was disclosed in the SDS for the solvents. Several other undisclosed components, including methanol, isopropanol and n-butanol, were also identified in the printing inks, fountain solutions and dilution solvents. We noted that, of the companies we surveyed, only 57.2% had a hazard communication program, 61.8% had SDSs on file and 59.9% provided employee safety and health training. We note that hazard communication programs were missing or ineffective in almost half of the 152 printing industries surveyed. Conclusions: Current safety information of solvents components in printing industries was inadequate, and many hazardous compounds were undisclosed in the SDSs of the solvents or the labels of the containers. The implementation of hazard communications in printing industries was still not enough for protecting the employees’ safety and health. PMID:26568584

Supercritical-Fluid Extraction of Oil From Tar Sands

NASA Technical Reports Server (NTRS)

Compton, L. E.

1982-01-01

New supercritical solvent mixtures have been laboratory-tested for extraction of oil from tar sands. Mixture is circulated through sand at high pressure and at a temperature above critical point, dissolving organic matter into the compressed gas. Extract is recovered from sand residues. Low-temperature super-critical solvents reduce energy consumption and waste-disposal problems.

Method of filtering a target compound from a first solvent that is above its critical density

DOEpatents

Phelps, Max R [Richland, WA; Yonker, Clement R [Kennewick, WA; Fulton, John L [Richland, WA; Bowman, Lawrence E [Richland, WA

2001-07-24

The present invention is a method of separating a first compound having a macromolecular structure from a mixture. The first solvent is a fluid that is a gas at standard temperature and pressure and is at a density greater than a critical density of the fluid. A macromolecular structure containing a first compound is dissolved therein as a mixture. The mixture is contacted onto a selective barrier and the first solvent passed through the selective barrier thereby retaining the first compound, followed by recovering the first compound. By using a fluid that is a gas at standard temperature and pressure at a density greater than its critical density, separation without depressurization is fast and efficient.

Application of chiral critical clusters to assymetric synthesis

DOEpatents

Ferrieri, Richard A.

2002-01-01

Disclosed is a composition, a method of making and a method of using critical clusters for asymmetric synthesis using substantially optically-pure chiral solvent molecules in a supercritical fluid. The solvent molecules are capable of forming a multipoint hydrogen bonded solvate as they encage at least one solute molecule. The encaged solute molecule is capable of reacting to form an optically active chiral center. In another aspect, there is disclosed a method of directing the position of bonding between a solute molecule and a ligand involving encaging the solute molecule and the ligand with polar solvent molecules in a supercritical fluid under conditions of temperature and pressure sufficient to change electric charge distribution in the solute molecule. In yet another aspect, disclosed is a method of making pharmaceutical compounds involving encaging a solute molecule, which is capable of forming a chiral center, and a ligand with polar solvent molecules in a supercritical fluid under conditions of temperature and pressure sufficient to change electric charge distribution of the solute molecule. The solute molecule and ligand are then reacted whereby the ligand bonds to the solute molecule forming a chiral center. Also disclosed is a method for racemic resolution using critical clusters involving encaging racemic mixtures of solute molecules with substantially optically-pure chiral solvent molecules in a supercritical fluid under conditions of temperature and pressure sufficient to form critical clusters. The solvent molecules are capable of multipoint hydrogen bonding with the solute molecules. The encaged solute molecules are then nonenzymatically reacted to enhance the optical purity of the solute molecules.

Determination of residual solvents and investigation of their effect on ampicillin trihydrate crystal structure.

PubMed

Nojavan, Saeed; Ghassempour, Alireza; Bashour, Yosef; Darbandi, Masoud Khalilian; Ahmadi, Seyyed Hamid

2005-01-04

In the present work, the relationship between residual solvents concentration and ampicillin trihydrate crystals stability has been investigated. The amounts of residual solvents determined by GC, X-ray powder diffraction (XRPD) and Fourier transform infrared spectroscopy (FT-IR) were used for characterization of solid state. The obtained results have shown good relationship between concentration of methylene chloride (as a critical residue solvent) and degree of ampicillin trihydrate crystallinity. As with the increasing methylene chloride concentration in the sample the degree of crystallinity decreased after stability test. From this relationship, critical concentration of methylene chloride into the ampicillin trihydrate is obtained and the results can be used for improving the large-scale production of ampicillin trihydrate.

Breakup of a liquid rivulet falling over an inclined plate: Identification of a critical Weber number

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

Singh, Rajesh K.; Galvin, Janine E.; Whyatt, Greg A.

2017-05-01

We have numerically investigated the breakup of a rivulet falling over a smooth inclined plate using the volume of fluid method. The breakup the rivulet is a complex phenomenon that is dictated by many factors, such as solvent properties, contact angle, inertia, plate inclination, etc. An extensive simulation campaign was conducted wherein these factors were systematically investigated. Regimes for a stable rivulet and an unstable rivulet that leads to the breakup and formation of a droplet are examined in terms of a critical value of the Weber number (Wecr) that delineates these regimes. The effect of plate inclination on themore » breakup of the rivulet shows that the critical Weber number decreases with increased inclination angle () owing to higher liquid velocity. However, the effect is negligible beyond >60. The impact of solvent properties is characterized using the Kapitza number (Ka). Variation of Wecr with Ka shows two trends depending on the Ka value of the solvent. Solvents with lower Ka values, corresponding to high viscosities and/or low surface tensions, show smaller values of the critical Weber number and the variation is linear. While solvents with higher Ka values exhibit higher values of the Wecr and the variation in Wecr is steep. This behavior is more pronounced with increasing contact angle. Higher contact angles promote rivulet breakup so that inertia must be higher to the breakup. A phenomenological scaling for a critical Weber number with the Kapitza number and contact angle is presented that can offer insight into rivulet breakup.« less

Critical Casimir effect in a polymer chain in supercritical solvents.

PubMed

Sumi, Tomonari; Imazaki, Nobuyuki; Sekino, Hideo

2009-03-01

Density fluctuation effects on the conformation of a polymer chain in a supercritical solvent were investigated by performing a multiscale simulation based on the density-functional theory. We found (a) a universal swelling of the polymer chain near the critical point, irrespective of whether the polymer chain is solvophilic or solvophobic, and (b) a characteristic collapse of the polymer chain having a strong solvophilicity at a temperature slightly higher than the critical point, where the isothermal compressibility becomes less than the ideal one.

Solvent induced modifications to fiber nanostructure and morphology for 12HSA molecular gels

NASA Astrophysics Data System (ADS)

Gao, Jie

Molecular organogels are thermo reversible quasi-solid materials, which are formed by low molecular weight organogelators (LMOGs) undergoing supramolecular aggregation via non-covalent interactions, forming a three-dimensional fibrillar network. Numerous applications of molecular organogels are been investigated as edible oils, drug release matrices and personal care products. The chemistry of the organic phase (i.e., solvent) influences every level of structure in organogels. Different solvents induce LMOG to assemble into "crystal like" fibers, which have more than one crystal form, lamellar arrangement and domain size. Differences in these solid states are known to affect the macroscopic properties of the gel, including critical gelator concentration (CGC), melting point, melting enthalpy and opacity.12-hydroxystearic acid (12HSA) was examined in several classes of organic solvents with different function groups. These gels, sols or precipitates were analyzed using a series of techniques including: powder x-ray diffraction (XRD), differential scanning calorimetry (DSC), fourier-transform infrared spectroscopy (FT-IR), pulsed nuclear magnetic resonance spectroscopy (pNMR) and microscopy. Specifically, certain solvents caused 12HSA to self-assemble into a triclinic parallel polymorphic form with subcell spacing of ~4.6, 3.9, and 3.8 A and an interdigitated unit cell with a lamellar arrangement (38~44 A). This polymorphic form corresponded to a less effective sphereultic supramolecular crystalline network, which immobilizes solvents at CGC greater than 1.5 wt %. The other group of solvents induce a hexagonal subcell spacing (i.e., unit sub cell spacing ~4.1 A) and are arranged in a multi lamellar fashion with a unit cell greater than the bimolecular length of 12HSA (~54 A).This polymorphic form corresponds to fibrillar aggregates with a CGC less than 1 wt %.

Flory-type theories of polymer chains under different external stimuli

NASA Astrophysics Data System (ADS)

Budkov, Yu A.; Kiselev, M. G.

2018-01-01

In this Review, we present a critical analysis of various applications of the Flory-type theories to a theoretical description of the conformational behavior of single polymer chains in dilute polymer solutions under a few external stimuli. Different theoretical models of flexible polymer chains in the supercritical fluid are discussed and analysed. Different points of view on the conformational behavior of the polymer chain near the liquid-gas transition critical point of the solvent are presented. A theoretical description of the co-solvent-induced coil-globule transitions within the implicit-solvent-explicit-co-solvent models is discussed. Several explicit-solvent-explicit-co-solvent theoretical models of the coil-to-globule-to-coil transition of the polymer chain in a mixture of good solvents (co-nonsolvency) are analysed and compared with each other. Finally, a new theoretical model of the conformational behavior of the dielectric polymer chain under the external constant electric field in the dilute polymer solution with an explicit account for the many-body dipole correlations is discussed. The polymer chain collapse induced by many-body dipole correlations of monomers in the context of statistical thermodynamics of dielectric polymers is analysed.

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

DOE PAGES

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

2017-08-18

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

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

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

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

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

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

Singh, Rajesh K.; Galvin, Janine E.; Sun, Xin

We have numerically investigated the breakup of a rivulet falling over a smooth inclined plate using the volume of fluid method. The breakup the rivulet is a complex phenomenon that is dictated by many factors, such as solvent properties, contact angle, inertia, plate inclination, etc. An extensive simulation campaign was conducted wherein these factors were systematically investigated. Regimes for a stable rivulet and an unstable rivulet that leads to the breakup and formation of a droplet are examined in terms of a critical value of the Weber number (Wecr) that delineates these regimes. The effect of plate inclination on themore » breakup of the rivulet shows that the critical Weber number decreases with increased inclination angle () owing to higher liquid velocity. However, the effect is negligible beyond >60. The impact of solvent properties is characterized using the Kapitza number (Ka). Variation of Wecr with Ka shows two trends depending on the Ka value of the solvent. Solvents with lower Ka values, corresponding to high viscosities and/or low surface tensions, show smaller values of the critical Weber number and the variation is linear. While solvents with higher Ka values exhibit higher values of the Wecr and the variation in Wecr is steep. This behavior is more pronounced with increasing contact angle. Higher contact angles promote rivulet breakup so that inertia must be higher to the breakup. A phenomenological scaling for a critical Weber number with the Kapitza number and contact angle is presented that can offer insight into rivulet breakup.« less

Breakup of a liquid rivulet falling over an inclined plate: Identification of a critical Weber number

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

Singh, Rajesh K.; Galvin, Janine E.; Whyatt, Greg A.

Here, we have numerically investigated the breakup of a rivulet falling over a smooth inclined plate using the volume of fluid method. The breakup the rivulet is a complex phenomenon that is dictated by many factors, such as solvent properties, contact angle, inertia, plate inclination, etc. An extensive simulation campaign was conducted wherein these factors were systematically investigated. Regimes for a stable rivulet and an unstable rivulet that leads to the breakup and formation of a droplet are examined in terms of a critical value of the Weber number (We cr) that delineates these regimes. The effect of plate inclinationmore » on the breakup of the rivulet shows that the critical Weber number decreases with increased inclination angle (θ) owing to higher liquid velocity. However, the effect is negligible beyond θ > 60°. The impact of solvent properties is characterized using the Kapitza number (Ka). Variation of We cr with Ka shows two trends depending on the Ka value of the solvent. Solvents with lower Ka values, corresponding to high viscosities and/or low surface tensions, show smaller values of the critical Weber number and the variation is linear. While solvents with higher Ka values exhibit higher values of the We cr and the variation in We cr is steep. This behavior is more pronounced with increasing contact angle. Higher contact angles promote rivulet breakup so that inertia must be higher to the breakup. As a result, a phenomenological scaling for a critical Weber number with the Kapitza number and contact angle is presented that can offer insight into rivulet breakup.« less

Breakup of a liquid rivulet falling over an inclined plate: Identification of a critical Weber number

DOE PAGES

Singh, Rajesh K.; Galvin, Janine E.; Whyatt, Greg A.; ...

2017-05-04

Here, we have numerically investigated the breakup of a rivulet falling over a smooth inclined plate using the volume of fluid method. The breakup the rivulet is a complex phenomenon that is dictated by many factors, such as solvent properties, contact angle, inertia, plate inclination, etc. An extensive simulation campaign was conducted wherein these factors were systematically investigated. Regimes for a stable rivulet and an unstable rivulet that leads to the breakup and formation of a droplet are examined in terms of a critical value of the Weber number (We cr) that delineates these regimes. The effect of plate inclinationmore » on the breakup of the rivulet shows that the critical Weber number decreases with increased inclination angle (θ) owing to higher liquid velocity. However, the effect is negligible beyond θ > 60°. The impact of solvent properties is characterized using the Kapitza number (Ka). Variation of We cr with Ka shows two trends depending on the Ka value of the solvent. Solvents with lower Ka values, corresponding to high viscosities and/or low surface tensions, show smaller values of the critical Weber number and the variation is linear. While solvents with higher Ka values exhibit higher values of the We cr and the variation in We cr is steep. This behavior is more pronounced with increasing contact angle. Higher contact angles promote rivulet breakup so that inertia must be higher to the breakup. As a result, a phenomenological scaling for a critical Weber number with the Kapitza number and contact angle is presented that can offer insight into rivulet breakup.« less

Enzymatic temperature change indicator

DOEpatents

Klibanov, Alexander M.; Dordick, Jonathan S.

1989-01-21

A temperature change indicator is described which is composed of an enzyme and a substrate for that enzyme suspended in a solid organic solvent or mixture of solvents as a support medium. The organic solvent or solvents are chosen so as to melt at a specific temperature or in a specific temperature range. When the temperature of the indicator is elevated above the chosen, or critical temperature, the solid organic solvent support will melt, and the enzymatic reaction will occur, producing a visually detectable product which is stable to further temperature variation.

Evaluation of alternatives for trichlorotrifluoroethane (CFC-113) to clean and verify liquid oxygen systems

NASA Technical Reports Server (NTRS)

Morris, Michelle L.

1996-01-01

NASA Langley Research Center (LARC) investigated several alternatives to the use of tri-chloro-tri-fluoroethane(CFC-113) in oxygen cleaning and verification. Alternatives investigated include several replacement solvents, Non-Destructive Evaluation (NDE) and Total Organic Carbon (TOC) analysis. Among the solvents, 1, 1-dichloro-1-fluoroethane (HCFC 141b) and di-chloro-penta-fluoro-propane (HCFC 225) are the most suitable alternatives for cleaning and verification. However, use of HCFC 141b is restricted, HCFC 225 introduces toxicity hazards, and the NDE and TOC methods of verification are not suitable for processes at LaRC. Therefore, the interim recommendation is to sparingly use CFC-113 for the very difficult cleaning tasks where safety is critical and to use HCFC 225 to clean components in a controlled laboratory environment. Meanwhile, evaluation must continue on now solvents and procedures to find one suited to LaRCs oxygen cleaning needs.

The influence of solvent processing on polyester bioabsorbable polymers.

PubMed

Manson, Joanne; Dixon, Dorian

2012-01-01

Solvent-based methods are commonly employed for the production of polyester-based samples and coatings in both medical device production and research. The influence of solvent casting and subsequent drying time was studied using thermal analysis, spectroscopy and weight measurement for four grades of 50 : 50 poly(lactic-co-glycolic acid) (PLGA) produced by using chloroform, dichloromethane, and acetone. The results demonstrate that solvent choice and PLGA molecular weight are critical factors in terms of solvent removal rate and maintaining sample integrity, respectively. The protocols widely employed result in high levels of residual solvent and a new protocol is presented together with solutions to commonly encountered problems.

Glymes as Versatile Solvents for Chemical Reactions and Processes: from the Laboratory to Industry

PubMed Central

Tang, Shaokun; Zhao, Hua

2014-01-01

Glymes, also known as glycol diethers, are saturated non-cyclic polyethers containing no other functional groups. Most glymes are usually less volatile and less toxic than common laboratory organic solvents; in this context, they are more environmentally benign solvents. However, it is also important to point out that some glymes could cause long-term reproductive and developmental damages despite their low acute toxicities. Glymes have both hydrophilic and hydrophobic characters that common organic solvents are lack of. In addition, they are usually thermally and chemically stable, and can even form complexes with ions. Therefore, glymes are found in a broad range of laboratory applications including organic synthesis, electrochemistry, biocatalysis, materials, and Chemical Vapor Deposition (CVD), etc. In addition, glyme are used in numerous industrial applications, such as cleaning products, inks, adhesives and coatings, batteries and electronics, absorption refrigeration and heat pumps, as well as pharmaceutical formulations, etc. However, there is a lack of comprehensive and critical review on this attractive subject. This review aims to accomplish this task by providing an in-depth understanding of glymes’ physicochemical properties, toxicity and major applications. PMID:24729866

Process for forming transparent aerogel insulating arrays

DOEpatents

Tewari, Param H.; Hunt, Arlon J.

1986-01-01

An improved supercritical drying process for forming transparent silica aerogel arrays is described. The process is of the type utilizing the steps of hydrolyzing and condensing aloxides to form alcogels. A subsequent step removes the alcohol to form aerogels. The improvement includes the additional step, after alcogels are formed, of substituting a solvent, such as CO.sub.2, for the alcohol in the alcogels, the solvent having a critical temperature less than the critical temperature of the alcohol. The resulting gels are dried at a supercritical temperature for the selected solvent, such as CO.sub.2, to thereby provide a transparent aerogel array within a substantially reduced (days-to-hours) time period. The supercritical drying occurs at about 40.degree. C. instead of at about 270.degree. C. The improved process provides increased yields of large scale, structurally sound arrays. The transparent aerogel array, formed in sheets or slabs, as made in accordance with the improved process, can replace the air gap within a double glazed window, for example, to provide a substantial reduction in heat transfer. The thus formed transparent aerogel arrays may also be utilized, for example, in windows of refrigerators and ovens, or in the walls and doors thereof or as the active material in detectors for analyzing high energy elementry particles or cosmic rays.

Process for forming transparent aerogel insulating arrays

DOEpatents

Tewari, P.H.; Hunt, A.J.

1985-09-04

An improved supercritical drying process for forming transparent silica aerogel arrays is described. The process is of the type utilizing the steps of hydrolyzing and condensing aloxides to form alcogels. A subsequent step removes the alcohol to form aerogels. The improvement includes the additional step, after alcogels are formed, of substituting a solvent, such as CO/sub 2/, for the alcohol in the alcogels, the solvent having a critical temperature less than the critical temperature of the alcohol. The resulting gels are dried at a supercritical temperature for the selected solvent, such as CO/sub 2/, to thereby provide a transparent aerogel array within a substantially reduced (days-to-hours) time period. The supercritical drying occurs at about 40/sup 0/C instead of at about 270/sup 0/C. The improved process provides increased yields of large scale, structurally sound arrays. The transparent aerogel array, formed in sheets or slabs, as made in accordance with the improved process, can replace the air gap within a double glazed window, for example, to provide a substantial reduction in heat transfer. The thus formed transparent aerogel arrays may also be utilized, for example, in windows of refrigerators and ovens, or in the walls and doors thereof or as the active material in detectors for analyzing high energy elementary particles or cosmic rays.

Temperature-dependent micellar structures in poly(styrene-b-isoprene) diblock copolymer solutions near the critical micelle temperature

NASA Astrophysics Data System (ADS)

Bang, Joona; Viswanathan, Karthik; Lodge, Timothy P.; Park, Moon Jeong; Char, Kookheon

2004-12-01

The temperature dependence of the micelle structures formed by poly(styrene-b-isoprene) (SI) diblock copolymers in the selective solvents diethyl phthalate (DEP) and tetradecane (C14), which are selective for the PS and PI blocks, respectively, have been investigated by small angle neutron scattering (SANS). Two nearly symmetric SI diblock copolymers, one with a perdeuterated PS block and the other with a perdeuterated PI block, were examined in both DEP and C14. The SANS scattering length density of the solvent was matched closely to either the core or the corona block. The resulting core and corona contrast data were fitted with a detailed model developed by Pedersen and co-workers. The fits provide quantitative information on micellar characteristics such as aggregation number, core size, overall size, solvent fraction in the core, and corona thickness. As temperature increases, the solvent selectivity decreases, leading to substantial solvent swelling of the core and a decrease in the aggregation number and core size. Both core and corona chains are able to relax their conformations near the critical micelle temperature due to a decrease in the interfacial tension, even though the corona chains are always under good solvent conditions.

Synthesis, stabilization, and characterization of metal nanoparticles

NASA Astrophysics Data System (ADS)

White, Gregory Von, II

Wet chemical synthesis techniques offer the ability to control various nanoparticle characteristics including size, shape, dispersibility in both aqueous and organic solvents, and tailored surface chemistries appropriate for different applications. Large quantities of stabilizing ligands or surfactants are often required during synthesis to achieve these nanoparticle characteristics. Unfortunately, excess reaction byproducts, surfactants, and ligands remaining in solution after nanoparticle synthesis can impede application, and therefore post-synthesis purification must be employed. A liquid-liquid solvent/antisolvent pair (typically ethanol/toluene or ethanol/hexane for gold nanoparticles, GNPs) can be used to both purify and size-selectively fractionate hydrophobically modified nanoparticles. Alternatively, carbon dioxide may be used in place of a liquid antisolvent, a "green" approach, enabling both nanoparticle purification and size-selective fractionation while simultaneously eliminating mixed solvent waste and allowing solvent recycle. We have used small-angle neutron scattering (SANS) to investigate the ligand structure and composition response of alkanethiol modified gold and silver nanoparticles at varying anti-solvent conditions (CO2 or ethanol). The ligand lengths and ligand solvation for alkanethiol gold and silver NPs were found to decrease with increased antisolvent concentrations directly impacting their dispersibility in solution. Calculated Flory-Huggins interaction parameters support our SANS study for dodecanethiol dispersibility in the mixed organic solvents. This research has led to a greater understanding of the liquid-liquid precipitation process for metal nanoparticles, and provides critical results for future interaction energy modeling.

NOVEL POLYMERIC MEMBRANE FOR DEHYDRATION OF ORGANIC SOLVENTS

EPA Science Inventory

Pervaporation has emerged as an economically viable alternative technology for dehydration of organic solvents, removal of organic compounds and organic/organic separations. Development of a membrane system with suitable flux and selectivity characteristics plays a critical role...

Approaches to efficiently estimate solvation and explicit water energetics in ligand binding: the use of WaterMap [WaterMap and Its Implementation in Drug Discovery

DOE PAGES

Yang, Yue; Wong, Sergio E.; Lightstone, Felice C.

2012-09-08

Solvents play quite an important role in most chemical and biological processes. It is widely accepted that the presence of water or other solvents in many chemical reactions can result in much lower energy barrier. In enzymatic catalysis, water mediated reaction pathways have been observed in various studies. In addition, different conformation flexibility and hydrogen bond patterns have been discovered for cyclic peptides in the presence of membrane and water, further illustrating the impact of solvent in biological activities such like membrane penetration. moreover, as will be discussed later in this review, water also plays a critical role in host-guestmore » chemistry and thus is essential to drug design. As such, it is not surprising that accounting for solvents is critical in drug discovery since drugs must modulate biological systems.« less

Preparation of titanium oxide ceramic membranes

DOEpatents

Anderson, Marc A.; Xu, Qunyin

1992-01-01

A procedure is disclosed for the reliable production of either particulate or polymeric titanium ceramic membranes by a highly constrained sol-gel procedure. The critical constraints in the procedure include the choice of alkyl alcohol solvent, the amount of water and its rate of addition, the pH of the solution during hydrolysis, and the limit of sintering temperature applied to the resulting gels.

Preparation of titanium oxide ceramic membranes

DOEpatents

Anderson, M.A.; Xu, Q.

1992-03-17

A procedure is disclosed for the reliable production of either particulate or polymeric titanium ceramic membranes by a highly constrained sol-gel procedure. The critical constraints in the procedure include the choice of alkyl alcohol solvent, the amount of water and its rate of addition, the pH of the solution during hydrolysis, and the limit of sintering temperature applied to the resulting gels.

Critical conditions of polymer adsorption and chromatography on non-porous substrates.

PubMed

Cimino, Richard T; Rasmussen, Christopher J; Brun, Yefim; Neimark, Alexander V

2016-07-15

We present a novel thermodynamic theory and Monte Carlo simulation model for adsorption of macromolecules to solid surfaces that is applied for calculating the chain partition during separation on chromatographic columns packed with non-porous particles. We show that similarly to polymer separation on porous substrates, it is possible to attain three chromatographic modes: size exclusion chromatography at very weak or no adsorption, liquid adsorption chromatography when adsorption effects prevail, and liquid chromatography at critical conditions that occurs at the critical point of adsorption. The main attention is paid to the analysis of the critical conditions, at which the retention is chain length independent. The theoretical results are verified with specially designed experiments on isocratic separation of linear polystyrenes on a column packed with non-porous particles at various solvent compositions. Without invoking any adjustable parameters related to the column and particle geometry, we describe quantitatively the observed transition between the size exclusion and adsorption separation regimes upon the variation of solvent composition, with the intermediate mode occurring at a well-defined critical point of adsorption. A relationship is established between the experimental solvent composition and the effective adsorption potential used in model simulations. Copyright © 2016 Elsevier Inc. All rights reserved.

Computational and theoretical studies of globular proteins

NASA Astrophysics Data System (ADS)

Pagan, Daniel L.

Protein crystallization is often achieved in experiment through a trial and error approach. To date, there exists a dearth of theoretical understanding of the initial conditions necessary to promote crystallization. While a better understanding of crystallization will help to create good crystals suitable for structure analysis, it will also allow us to prevent the onset of certain diseases. The core of this thesis is to model and, ultimately, understand the phase behavior of protein particles in solution. Toward this goal, we calculate the fluid-fluid coexistence curve in the vicinity of the metastable critical point of the modified Lennard-Jones potential, where it has been shown that nucleation is increased by many orders of magnitude. We use finite-size scaling techniques and grand canonical Monte Carlo simulation methods. This has allowed us to pinpoint the critical point and subcritical region with high accuracy in spite of the critical fluctuations that hinder sampling using other Monte Carlo techniques. We also attempt to model the phase behavior of the gamma-crystallins, mutations of which have been linked to genetic cataracts. The complete phase behavior of the square well potential at the ranges of attraction lambda = 1.15 and lambda = 1.25 is calculated and compared with that of the gammaII-crystallin. The role of solvent is also important in the crystallization process and affects the phase behavior of proteins in solution. We study a model that accounts for the contribution of the solvent free-energy to the free-energy of globular proteins. This model allows us to model phase behavior that includes solvent.

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.

Thermodynamic Approach to Boron Nitride Nanotube Solubility and Dispersion

NASA Technical Reports Server (NTRS)

Tiano, A. L.; Gibbons, L.; Tsui, M.; Applin, S. I.; Silva, R.; Park, C.; Fay, C. C.

2016-01-01

Inadequate dispersion of nanomaterials is a critical issue that significantly limits the potential properties of nanocomposites and when overcome, will enable further enhancement of material properties. The most common methods used to improve dispersion include surface functionalization, surfactants, polymer wrapping, and sonication. Although these approaches have proven effective, they often achieve dispersion by altering the surface or structure of the nanomaterial and ultimately, their intrinsic properties. Co-solvents are commonly utilized in the polymer, paint, and art conservation industries to selectively dissolve materials. These co-solvents are utilized based on thermodynamic interaction parameters and are chosen so that the original materials are not affected. The same concept was applied to enhance the dispersion of boron nitride nanotubes (BNNTs) to facilitate the fabrication of BNNT nanocomposites. Of the solvents tested, dimethylacetamide (DMAc) exhibited the most stable, uniform dispersion of BNNTs, followed by N,N-dimethylformamide (DMF), acetone, and N-methyl-2-pyrrolidone (NMP). Utilizing the known Hansen solubility parameters of these solvents in comparison to the BNNT dispersion state, a region of good solubility was proposed. This solubility region was used to identify co-solvent systems that led to improved BNNT dispersion in poor solvents such as toluene, hexane, and ethanol. Incorporating the data from the co-solvent studies further refined the proposed solubility region. From this region, the Hansen solubility parameters for BNNTs are thought to lie at the midpoint of the solubility sphere: 16.8, 10.7, and 9.0 MPa(exp 1/2) for delta d, delta p, and delta h, respectively, with a calculated Hildebrand parameter of 21.8 MPa)exp 1/2).

Thermodynamic approach to boron nitride nanotube solubility and dispersion.

PubMed

Tiano, A L; Gibbons, L; Tsui, M; Applin, S I; Silva, R; Park, C; Fay, C C

2016-02-21

Inadequate dispersion of nanomaterials is a critical issue that significantly limits the potential properties of nanocomposites and when overcome, will enable further enhancement of material properties. The most common methods used to improve dispersion include surface functionalization, surfactants, polymer wrapping, and sonication. Although these approaches have proven effective, they often achieve dispersion by altering the surface or structure of the nanomaterial and ultimately, their intrinsic properties. Co-solvents are commonly utilized in the polymer, paint, and art conservation industries to selectively dissolve materials. These co-solvents are utilized based on thermodynamic interaction parameters and are chosen so that the original materials are not affected. The same concept was applied to enhance the dispersion of boron nitride nanotubes (BNNTs) to facilitate the fabrication of BNNT nanocomposites. Of the solvents tested, dimethylacetamide (DMAc) exhibited the most stable, uniform dispersion of BNNTs, followed by N,N-dimethylformamide (DMF), acetone, and N-methyl-2-pyrrolidone (NMP). Utilizing the known Hansen solubility parameters of these solvents in comparison to the BNNT dispersion state, a region of good solubility was proposed. This solubility region was used to identify co-solvent systems that led to improved BNNT dispersion in poor solvents such as toluene, hexane, and ethanol. Incorporating the data from the co-solvent studies further refined the proposed solubility region. From this region, the Hansen solubility parameters for BNNTs are thought to lie at the midpoint of the solubility sphere: 16.8, 10.7, and 9.0 MPa(1/2) for δd, δp, and δh, respectively, with a calculated Hildebrand parameter of 21.8 MPa(1/2).

Competitive interactions and controlled release of a natural antioxidant from halloysite nanotubes.

PubMed

Hári, József; Gyürki, Ádám; Sárközi, Márk; Földes, Enikő; Pukánszky, Béla

2016-01-15

Halloysite nanotubes used as potential carrier material for a controlled release stabilizer in polyethylene were thoroughly characterized with several techniques including the measurement of specific surface area, pore volume and surface energy. The high surface energy of the halloysite results in the strong bonding of the additive to the surface. Dissolution experiments carried out with eight different solvents for the determination of the effect of solvent characteristics on the amount of irreversibly bonded quercetin proved that adsorption and dissolution depend on competitive interactions prevailing in the system. Solvents with low polarity dissolve only surplus quercetin adsorbed in multilayers. Polyethylene is a very apolar polymer forming weak interactions with every substance; quercetin dissolves into it from the halloysite surface only above a critical surface coverage. Stabilization experiments confirmed that strong adhesion prevents dissolution and results in limited stabilization efficiency. At larger adsorbed amounts better stability and extended effect were measured indicating dissolution and controlled release. Copyright © 2015 Elsevier Inc. All rights reserved.

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

Evaluating the Properties of Poly(lactic-co-glycolic acid) Nanoparticle Formulations Encapsulating a Hydrophobic Drug by Using the Quality by Design Approach.

PubMed

Kozaki, Masato; Kobayashi, Shin-Ichiro; Goda, Yukihiro; Okuda, Haruhiro; Sakai-Kato, Kumiko

2017-01-01

We applied the Quality by Design (QbD) approach to the development of poly(lactic-co-glycolic acid) (PLGA) nanoparticle formulations encapsulating triamcinolone acetonide, and the critical process parameters (CPPs) were identified to clarify the correlations between critical quality attributes and CPPs. Quality risk management was performed by using an Ishikawa diagram and experiments with a fractional factorial design (ANOVA). The CPPs for particle size were PLGA concentration and rotation speed, and the CPP for relative drug loading efficiency was the poor solvent to good solvent volume ratio. By assessing the mutually related factors in the form of ratios, many factors could be efficiently considered in the risk assessment. We found a two-factor interaction between rotation speed and rate of addition of good solvent by using a fractional factorial design with resolution V. The system was then extended by using a central composite design, and the results obtained were visualized by using the response surface method to construct a design space. Our research represents a case study of the application of the QbD approach to pharmaceutical development, including formulation screening, by taking actual production factors into consideration. Our findings support the feasibility of using a similar approach to nanoparticle formulations under development. We could establish an efficient method of analyzing the CPPs of PLGA nanoparticles by using a QbD approach.

Volatile Solvents as Drugs of Abuse: Focus on the Cortico-Mesolimbic Circuitry

PubMed Central

Beckley, Jacob T; Woodward, John J

2013-01-01

Volatile solvents such as those found in fuels, paints, and thinners are found throughout the world and are used in a variety of industrial applications. However, these compounds are also often intentionally inhaled at high concentrations to produce intoxication. While solvent use has been recognized as a potential drug problem for many years, research on the sites and mechanisms of action of these compounds lags behind that of other drugs of abuse. In this review, we first discuss the epidemiology of voluntary solvent use throughout the world and then consider what is known about their basic pharmacology and how this may explain their use as drugs of abuse. We next present data from preclinical and clinical studies indicating that these substances induce common addiction sequelae such as dependence, withdrawal, and cognitive impairments. We describe how toluene, the most commonly studied psychoactive volatile solvent, alters synaptic transmission in key brain circuits such as the mesolimbic dopamine system and medial prefrontal cortex (mPFC) that are thought to underlie addiction pathology. Finally, we make the case that activity in mPFC circuits is a critical regulator of the mesolimbic dopamine system's ability to respond to volatile solvents like toluene. Overall, this review provides evidence that volatile solvents have high abuse liability because of their selective effects on critical nodes of the addiction neurocircuitry, and underscores the need for more research into how these compounds induce adaptations in neural circuits that underlie addiction pathology. PMID:23954847

Brownian motion of a nano-colloidal particle: the role of the solvent.

PubMed

Torres-Carbajal, Alexis; Herrera-Velarde, Salvador; Castañeda-Priego, Ramón

2015-07-15

Brownian motion is a feature of colloidal particles immersed in a liquid-like environment. Usually, it can be described by means of the generalised Langevin equation (GLE) within the framework of the Mori theory. In principle, all quantities that appear in the GLE can be calculated from the molecular information of the whole system, i.e., colloids and solvent molecules. In this work, by means of extensive Molecular Dynamics simulations, we study the effects of the microscopic details and the thermodynamic state of the solvent on the movement of a single nano-colloid. In particular, we consider a two-dimensional model system in which the mass and size of the colloid are two and one orders of magnitude, respectively, larger than the ones associated with the solvent molecules. The latter ones interact via a Lennard-Jones-type potential to tune the nature of the solvent, i.e., it can be either repulsive or attractive. We choose the linear momentum of the Brownian particle as the observable of interest in order to fully describe the Brownian motion within the Mori framework. We particularly focus on the colloid diffusion at different solvent densities and two temperature regimes: high and low (near the critical point) temperatures. To reach our goal, we have rewritten the GLE as a second kind Volterra integral in order to compute the memory kernel in real space. With this kernel, we evaluate the momentum-fluctuating force correlation function, which is of particular relevance since it allows us to establish when the stationarity condition has been reached. Our findings show that even at high temperatures, the details of the attractive interaction potential among solvent molecules induce important changes in the colloid dynamics. Additionally, near the critical point, the dynamical scenario becomes more complex; all the correlation functions decay slowly in an extended time window, however, the memory kernel seems to be only a function of the solvent density. Thus, the explicit inclusion of the solvent in the description of Brownian motion allows us to better understand the behaviour of the memory kernel at those thermodynamic states near the critical region without any further approximation. This information is useful to elaborate more realistic descriptions of Brownian motion that take into account the particular details of the host medium.

Effects of Solvents on Craze Initiation and Crack Propagation in Transparent Polymers

DTIC Science & Technology

1989-04-01

methyl methacrylate) ( PMMA ) materials, as well as several formulations of polycarbon- ate, show a range of critical strain measurements in crazing...propagation in transparent polymers is demonstrated by a dead weight loading apparatus and compact tension specimens based on ASTM E 399. Samples of PMMA ...environment. This includes the ability to be decontaminated. Polycarbonate (PC) and poly(methyl methacrylate) ( PMMA ) are known to craze while undfer

Ionic liquid solutions as extractive solvents for value-added compounds from biomass

PubMed Central

Passos, Helena; Freire, Mara G.; Coutinho, João A. P.

2014-01-01

In the past few years, the number of studies regarding the application of ionic liquids (ILs) as alternative solvents to extract value-added compounds from biomass has been growing. Based on an extended compilation and analysis of the data hitherto reported, the main objective of this review is to provide an overview on the use of ILs and their mixtures with molecular solvents for the extraction of value-added compounds present in natural sources. The ILs (or IL solutions) investigated as solvents for the extraction of natural compounds, such as alkaloids, flavonoids, terpenoids, lipids, among others, are outlined. The extraction techniques employed, namely solid–liquid extraction, and microwave-assisted and ultrasound-assisted extractions, are emphasized and discussed in terms of extraction yields and purification factors. Furthermore, the evaluation of the IL chemical structure and the optimization of the process conditions (IL concentration, temperature, biomass–solvent ratio, etc.) are critically addressed. Major conclusions on the role of the ILs towards the extraction mechanisms and improved extraction yields are additionally provided. The isolation and recovery procedures of the value-added compounds are ascertained as well as some scattered strategies already reported for the IL solvent recovery and reusability. Finally, a critical analysis on the economic impact versus the extraction performance of IL-based methodologies was also carried out and is here presented and discussed. PMID:25516718

Ionic liquid solutions as extractive solvents for value-added compounds from biomass.

PubMed

Passos, Helena; Freire, Mara G; Coutinho, João A P

2014-12-01

In the past few years, the number of studies regarding the application of ionic liquids (ILs) as alternative solvents to extract value-added compounds from biomass has been growing. Based on an extended compilation and analysis of the data hitherto reported, the main objective of this review is to provide an overview on the use of ILs and their mixtures with molecular solvents for the extraction of value-added compounds present in natural sources. The ILs (or IL solutions) investigated as solvents for the extraction of natural compounds, such as alkaloids, flavonoids, terpenoids, lipids, among others, are outlined. The extraction techniques employed, namely solid-liquid extraction, and microwave-assisted and ultrasound-assisted extractions, are emphasized and discussed in terms of extraction yields and purification factors. Furthermore, the evaluation of the IL chemical structure and the optimization of the process conditions (IL concentration, temperature, biomass-solvent ratio, etc.) are critically addressed. Major conclusions on the role of the ILs towards the extraction mechanisms and improved extraction yields are additionally provided. The isolation and recovery procedures of the value-added compounds are ascertained as well as some scattered strategies already reported for the IL solvent recovery and reusability. Finally, a critical analysis on the economic impact versus the extraction performance of IL-based methodologies was also carried out and is here presented and discussed.

A generalized method for alignment of block copolymer films: solvent vapor annealing with soft shear.

PubMed

Qiang, Zhe; Zhang, Yuanzhong; Groff, Jesse A; Cavicchi, Kevin A; Vogt, Bryan D

2014-08-28

One of the key issues associated with the utilization of block copolymer (BCP) thin films in nanoscience and nanotechnology is control of their alignment and orientation over macroscopic dimensions. We have recently reported a method, solvent vapor annealing with soft shear (SVA-SS), for fabricating unidirectional alignment of cylindrical nanostructures. This method is a simple extension of the common SVA process by adhering a flat, crosslinked poly(dimethylsiloxane) (PDMS) pad to the BCP thin film. The impact of processing parameters, including annealing time, solvent removal rate and the physical properties of the PDMS pad, on the quality of alignment quantified by the Herman's orientational factor (S) is systematically examined for a model system of polystyrene-block-polyisoprene-block-polystyrene (SIS). As annealing time increases, the SIS morphology transitions from isotropic rods to highly aligned cylinders. Decreasing the rate of solvent removal, which impacts the shear rate imposed by the contraction of the PDMS, improves the orientation factor of the cylindrical domains; this suggests the nanostructure alignment is primarily induced by contraction of PDMS during solvent removal. Moreover, the physical properties of the PDMS controlled by the crosslink density impact the orientation factor by tuning its swelling extent during SVA-SS and elastic modulus. Decreasing the PDMS crosslink density increases S; this effect appears to be primarily driven by the changes in the solubility of the SVA-SS solvent in the PDMS. With this understanding of the critical processing parameters, SVA-SS has been successfully applied to align a wide variety of BCPs including polystyrene-block-polybutadiene-block-polystyrene (SBS), polystyrene-block-poly(N,N-dimethyl-n-octadecylammonium p-styrenesulfonate) (PS-b-PSS-DMODA), polystyrene-block-polydimethylsiloxane (PS-b-PDMS) and polystyrene-block-poly(2-vinlypyridine) (PS-b-P2VP). These results suggest that SVA-SS is a generalizable method for the alignment of BCP thin films.

Process for hydrogenation of hydrocarbon tars

DOEpatents

Dolbear, Geoffrey E.

1978-07-18

Hydrocarbon tars of high asphaltene content such as tars obtained from pyrolysis of coal are dissolved in a solvent formed from the hydrogenation of the coal tars, and the resultant mixture hydrogenated in the presence of a catalyst at a pressure from about 1500 to 5000 psig at a temperature from about 500.degree. F to about the critical temperature of the solvent to form a light hydrocarbon as a solvent for the tars. Hydrogen content is at least three times the amount of hydrogen consumed.

Sintering Kinetics of Inkjet Printed Conductive Silver Lines on Insulating Plastic Substrate

DOE PAGES

Zhou, Wenchao; List, III, Frederick Alyious; Duty, Chad E; ...

2015-01-24

This paper focuses on sintering kinetics of inkjet printed lines containing silver nanoparticles deposited on a plastic substrate. Upon heat treatment, the change of resistance in the printed lines was measured as a function of time and sintering temperatures from 150 to 200 C. A critical temperature was observed for the sintering process, beyond which there was no further reduction in resistance. Analysis shows the critical temperature correlates to the boiling point of the solvent, which is attributed to a liquid-mediated sintering mechanism. It is demonstrated that the sintering process shuts down after the solvent has completely evaporated.

Conventional and Accelerated-Solvent Extractions of Green Tea (Camellia sinensis) for Metabolomics-based Chemometrics

PubMed Central

Kellogg, Joshua J.; Wallace, Emily D.; Graf, Tyler N.; Oberlies, Nicholas H.; Cech, Nadja B.

2018-01-01

Metabolomics has emerged as an important analytical technique for multiple applications. The value of information obtained from metabolomics analysis depends on the degree to which the entire metabolome is present and the reliability of sample treatment to ensure reproducibility across the study. The purpose of this study was to compare methods of preparing complex botanical extract samples prior to metabolomics profiling. Two extraction methodologies, accelerated solvent extraction and a conventional solvent maceration, were compared using commercial green tea [Camellia sinensis (L.) Kuntze (Theaceae)] products as a test case. The accelerated solvent protocol was first evaluated to ascertain critical factors influencing extraction using a D-optimal experimental design study. The accelerated solvent and conventional extraction methods yielded similar metabolite profiles for the green tea samples studied. The accelerated solvent extraction yielded higher total amounts of extracted catechins, was more reproducible, and required less active bench time to prepare the samples. This study demonstrates the effectiveness of accelerated solvent as an efficient methodology for metabolomics studies. PMID:28787673

Removal of common organic solvents from aqueous waste streams via supercritical C02 extraction: a potential green approach to sustainable waste management in the pharmaceutical industry.

PubMed

Leazer, Johnnie L; Gant, Sean; Houck, Anthony; Leonard, William; Welch, Christopher J

2009-03-15

Supercritical CO2 extraction of aqueous streams is a convenient and effective method to remove commonly used solvents of varying polarities from aqueous waste streams. The resulting aqueous layers can potentially be sewered; whereas the organic layer can be recovered for potential reuse. Supercritical fluid extraction (SFE) is a technology that is increasingly being used in commercial processes (1). Supercritical fluids are well suited for extraction of a variety of media, including solids, natural products, and liquid products. Many supercritical fluids have low critical temperatures, allowing for extractions to be done at modestly low temperatures, thus avoiding any potential thermal decomposition of the solutes under study (2). Furthermore, the CO2 solvent strength is easily tuned by adjusting the density of the supercritical fluid (The density is proportional to the pressure of the extraction process). Since many supercritical fluids are gases at ambient temperature, the extract can be concentrated by simply venting the reaction mixture to a cyclone collection vessel, using appropriate safety protocols.

ISDP salt batch #2 supernate qualification

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

Peters, T. B.; Nash, C. A.; Fink, S. D.

2009-01-05

This report covers the laboratory testing and analyses of the second Integrated Salt Disposition Project (ISDP) salt supernate samples, performed in support of initial radioactive operations of Actinide Removal Process (ARP) and Modular Caustic-Side Solvent Extraction Unit (MCU). Major goals of this work include characterizing Tank 22H supernate, characterizing Tank 41H supernate, verifying actinide and strontium adsorption with a standard laboratory-scale test using monosodium titanate (MST) and filtration, and checking cesium mass transfer behavior for the MCU solvent performance when contacted with the liquid produced from MST contact. This study also includes characterization of a post-blend Tank 49H sample asmore » part of the Nuclear Criticality Safety Evaluation (NCSE). This work was specified by Task Technical Request and by Task Technical and Quality Assurance Plan (TTQAP). In addition, a sampling plan will be written to guide analytical future work. Safety and environmental aspects of the work were documented in a Hazard Assessment Package.« less

Analysis of edible oil processing options for the BIO-Plex advanced life support system

NASA Technical Reports Server (NTRS)

Greenwalt, C. J.; Hunter, J.

2000-01-01

Edible oil is a critical component of the proposed plant-based Advanced Life Support (ALS) diet. Soybean, peanut, and single-cell oil are the oil source options to date. In terrestrial manufacture, oil is ordinarily extracted with hexane, an organic solvent. However, exposed solvents are not permitted in the spacecraft environment or in enclosed human tests by National Aeronautics and Space Administration due to their potential danger and handling difficulty. As a result, alternative oil-processing methods will need to be utilized. Preparation and recovery options include traditional dehulling, crushing, conditioning, and flaking, extrusion, pressing, water extraction, and supercritical extraction. These processing options were evaluated on criteria appropriate to the Advanced Life Support System and BIO-Plex application including: product quality, product stability, waste production, risk, energy needs, labor requirements, utilization of nonrenewable resources, usefulness of by-products, and versatility and mass of equipment to determine the most appropriate ALS edible oil-processing operation.

Innovative Alternative Technologies to Extract Carotenoids from Microalgae and Seaweeds

PubMed Central

Poojary, Mahesha M.; Barba, Francisco J.; Aliakbarian, Bahar; Donsì, Francesco; Pataro, Gianpiero; Dias, Daniel A.; Juliano, Pablo

2016-01-01

Marine microalgae and seaweeds (microalgae) represent a sustainable source of various bioactive natural carotenoids, including β-carotene, lutein, astaxanthin, zeaxanthin, violaxanthin and fucoxanthin. Recently, the large-scale production of carotenoids from algal sources has gained significant interest with respect to commercial and industrial applications for health, nutrition, and cosmetic applications. Although conventional processing technologies, based on solvent extraction, offer a simple approach to isolating carotenoids, they suffer several, inherent limitations, including low efficiency (extraction yield), selectivity (purity), high solvent consumption, and long treatment times, which have led to advancements in the search for innovative extraction technologies. This comprehensive review summarizes the recent trends in the extraction of carotenoids from microalgae and seaweeds through the assistance of different innovative techniques, such as pulsed electric fields, liquid pressurization, supercritical fluids, subcritical fluids, microwaves, ultrasounds, and high-pressure homogenization. In particular, the review critically analyzes technologies, characteristics, advantages, and shortcomings of the different innovative processes, highlighting the differences in terms of yield, selectivity, and economic and environmental sustainability. PMID:27879659

Generation of shrimp waste-based dispersant for oil spill response.

PubMed

Zhang, Kedong; Zhang, Baiyu; Song, Xing; Liu, Bo; Jing, Liang; Chen, Bing

2018-04-01

In this study, shrimp waste was enzymatically hydrolyzed to generate a green dispersant and the product was tested for crude oil dispersion in seawater. The hydrolysis process was first optimized based on the dispersant effectiveness (DE) of the product. The functional properties of the product were identified including stability, critical micelle concentration, and emulsification activity. Water was confirmed as a good solvent for dispersant generation when compared with three chemical solvents. The effects of salinity, mixing energy, and temperature on the dispersion of the Alaska North Slope (ANS) crude oil were examined. Microtox acute toxicity test was also conducted to evaluate the toxicity of the produced dispersant. In addition, DE of the product on three different types of crude oil, including ANS crude oil, Prudhoe Bay crude oil (PBC), and Arabian Light crude oil (ALC) was compared with that of the Corexit 9500, respectively. The research output could lead to a promising green solution to the oil spill problem and might result in many other environmental applications.

Innovative Alternative Technologies to Extract Carotenoids from Microalgae and Seaweeds.

PubMed

Poojary, Mahesha M; Barba, Francisco J; Aliakbarian, Bahar; Donsì, Francesco; Pataro, Gianpiero; Dias, Daniel A; Juliano, Pablo

2016-11-22

Marine microalgae and seaweeds (microalgae) represent a sustainable source of various bioactive natural carotenoids, including β-carotene, lutein, astaxanthin, zeaxanthin, violaxanthin and fucoxanthin. Recently, the large-scale production of carotenoids from algal sources has gained significant interest with respect to commercial and industrial applications for health, nutrition, and cosmetic applications. Although conventional processing technologies, based on solvent extraction, offer a simple approach to isolating carotenoids, they suffer several, inherent limitations, including low efficiency (extraction yield), selectivity (purity), high solvent consumption, and long treatment times, which have led to advancements in the search for innovative extraction technologies. This comprehensive review summarizes the recent trends in the extraction of carotenoids from microalgae and seaweeds through the assistance of different innovative techniques, such as pulsed electric fields, liquid pressurization, supercritical fluids, subcritical fluids, microwaves, ultrasounds, and high-pressure homogenization. In particular, the review critically analyzes technologies, characteristics, advantages, and shortcomings of the different innovative processes, highlighting the differences in terms of yield, selectivity, and economic and environmental sustainability.

Influence of solvent polarity and supersaturation on template-induced nucleation of carbamazepine crystal polymorphs

NASA Astrophysics Data System (ADS)

Parambil, Jose V.; Poornachary, Sendhil K.; Tan, Reginald B. H.; Heng, Jerry Y. Y.

2017-07-01

Studies on the use of template surfaces to induce heterogeneous crystal nucleation have gained momentum in recent years-with potential applications in selective crystallisation of polymorphs and in the generation of seed crystals in a continuous crystallisation process. In developing a template-assisted solution crystallisation process, the kinetics of homogeneous versus heterogeneous crystal nucleation could be influenced by solute-solvent, solute-template, and solvent-template interactions. In this study, we report the effect of solvents of varying polarity on the nucleation of carbamazepine (CBZ) crystal polymorphs, a model active pharmaceutical ingredient. The experimental results demonstrate that functionalised template surfaces are effective in promoting crystallisation of either the metastable (form II) or stable (form III) polymorphs of CBZ only in moderately (methanol, ethanol, isopropanol) and low polar (toluene) solvents. A solvent with high polarity (acetonitrile) is thought to mask the template effect on heterogeneous nucleation due to strong solute-solvent and solvent-template interactions. The current study highlights that a quality-by-design (QbD) approach-considering the synergistic effects of solute concentration, solvent type, solution temperature, and template surface chemistry on crystal nucleation-is critical to the development of a template-induced crystallisation process.

Optimization of flavanones extraction by modulating differential solvent densities and centrifuge temperatures.

PubMed

Chebrolu, Kranthi K; Jayaprakasha, G K; Jifon, J; Patil, Bhimanagouda S

2011-07-15

Understanding the factors influencing flavonone extraction is critical for the knowledge in sample preparation. The present study was focused on the extraction parameters such as solvent, heat, centrifugal speed, centrifuge temperature, sample to solvent ratio, extraction cycles, sonication time, microwave time and their interactions on sample preparation. Flavanones were analyzed in a high performance liquid chromatography (HPLC) and later identified by liquid chromatography and mass spectrometry (LC-MS). The five flavanones were eluted by a binary mobile phase with 0.03% phosphoric acid and acetonitrile in 20 min and detected at 280 nm, and later identified by mass spectral analysis. Dimethylsulfoxide (DMSO) and dimethyl formamide (DMF) had optimum extraction levels of narirutin, naringin, neohesperidin, didymin and poncirin compared to methanol (MeOH), ethanol (EtOH) and acetonitrile (ACN). Centrifuge temperature had a significant effect on flavanone distribution in the extracts. The DMSO and DMF extracts had homogeneous distribution of flavanones compared to MeOH, EtOH and ACN after centrifugation. Furthermore, ACN showed clear phase separation due to differential densities in the extracts after centrifugation. The number of extraction cycles significantly increased the flavanone levels during extraction. Modulating the sample to solvent ratio increased naringin quantity in the extracts. Current research provides critical information on the role of centrifuge temperature, extraction solvent and their interactions on flavanone distribution in extracts. Published by Elsevier B.V.

Supercritical extraction of lycopene from tomato industrial wastes with ethane.

PubMed

Nobre, Beatriz P; Gouveia, Luisa; Matos, Patricia G S; Cristino, Ana F; Palavra, António F; Mendes, Rui L

2012-07-11

Supercritical fluid extraction of all-E-lycopene from tomato industrial wastes (mixture of skins and seeds) was carried out in a semi-continuous flow apparatus using ethane as supercritical solvent. The effect of pressure, temperature, feed particle size, solvent superficial velocity and matrix initial composition was evaluated. Moreover, the yield of the extraction was compared with that obtained with other supercritical solvents (supercritical CO₂ and a near critical mixture of ethane and propane). The recovery of all-E-lycopene increased with pressure, decreased with the increase of the particle size in the initial stages of the extraction and was not practically affected by the solvent superficial velocity. The effect of the temperature was more complex. When the temperature increased from 40 to 60 °C the recovery of all-E-lycopene increased from 80 to 90%. However, for a further increase to 80 °C, the recovery remained almost the same, indicating that some E-Z isomerization could have occurred, as well as some degradation of lycopene. The recovery of all-E-lycopene was almost the same for feed samples with different all-E-lycopene content. Furthermore, when a batch with a higher all-E-lycopene content was used, supercritical ethane and a near critical mixture of ethane and propane showed to be better solvents than supercritical CO₂ leading to a faster extraction with a higher recovery of the carotenoid.

Conventional and accelerated-solvent extractions of green tea (camellia sinensis) for metabolomics-based chemometrics.

PubMed

Kellogg, Joshua J; Wallace, Emily D; Graf, Tyler N; Oberlies, Nicholas H; Cech, Nadja B

2017-10-25

Metabolomics has emerged as an important analytical technique for multiple applications. The value of information obtained from metabolomics analysis depends on the degree to which the entire metabolome is present and the reliability of sample treatment to ensure reproducibility across the study. The purpose of this study was to compare methods of preparing complex botanical extract samples prior to metabolomics profiling. Two extraction methodologies, accelerated solvent extraction and a conventional solvent maceration, were compared using commercial green tea [Camellia sinensis (L.) Kuntze (Theaceae)] products as a test case. The accelerated solvent protocol was first evaluated to ascertain critical factors influencing extraction using a D-optimal experimental design study. The accelerated solvent and conventional extraction methods yielded similar metabolite profiles for the green tea samples studied. The accelerated solvent extraction yielded higher total amounts of extracted catechins, was more reproducible, and required less active bench time to prepare the samples. This study demonstrates the effectiveness of accelerated solvent as an efficient methodology for metabolomics studies. Copyright © 2017. Published by Elsevier B.V.

Replacement solvents for use in chemical synthesis

DOEpatents

Molnar, Linda K.; Hatton, T. Alan; Buchwald, Stephen L.

2001-05-15

Replacement solvents for use in chemical synthesis include polymer-immobilized solvents having a flexible polymer backbone and a plurality of pendant groups attached onto the polymer backbone, the pendant groups comprising a flexible linking unit bound to the polymer backbone and to a terminal solvating moiety. The polymer-immobilized solvent may be dissolved in a benign medium. Replacement solvents for chemical reactions for which tetrahydrofuran or diethyl may be a solvent include substituted tetrahydrofurfuryl ethers and substituted tetrahydro-3-furan ethers. The replacement solvents may be readily recovered from the reaction train using conventional methods.

Percolation characteristics of solvent invasion in rough fractures under miscible conditions

NASA Astrophysics Data System (ADS)

Korfanta, M.; Babadagli, T.; Develi, K.

2017-10-01

Surface roughness and flow rate effects on the solvent transport under miscible conditions in a single fracture are studied. Surface replicas of seven different rocks (marble, granite, and limestone) are used to represent different surface roughness characteristics each described by different mathematical models including three fractal dimensions. Distribution of dyed solvent is investigated at various flow rate conditions to clarify the effect of roughness on convective and diffusive mixing. After a qualitative analysis using comparative images of different rocks, the area covered by solvent with respect to time is determined to conduct a semi-quantitative analysis. In this exercise, two distinct zones are identified, namely the straight lines obtained for convective (early times) and diffusive (late times) flow. The bending point between these two lines is used to point the transition between the two zones. Finally, the slopes of the straight lines and the bending points are correlated to five different roughness parameters and the rate (Peclet number). It is observed that both surface roughness and flow rate have significant effect on solvent spatial distribution. The largest area covered is obtained at moderate flow rates and hence not only the average surface roughness characteristic is important, but coessentially total fracture surface area needs to be considered when evaluating fluid distribution. It is also noted that the rate effect is critically different for the fracture samples of large grain size (marbles and granite) compared to smaller grain sizes (limestones). Variogram fractal dimension exhibits the strongest correlation with the maximum area covered by solvent, and display increasing trend at the moderate flow rates. Equations with variogram surface fractal dimension in combination with any other surface fractal parameter coupled with Peclet number can be used to predict maximum area covered by solvent in a single fracture, which in turn can be utilized to model oil recovery, waste disposal, and groundwater contamination processes in the presence of fractures.

Method for the preparation of high surface area high permeability carbons

DOEpatents

Lagasse, Robert R.; Schroeder, John L.

1999-05-11

A method for preparing carbon materials having high surface area and high macropore volume to provide high permeability. These carbon materials are prepared by dissolving a carbonizable polymer precursor, in a solvent. The solution is cooled to form a gel. The solvent is extracted from the gel by employing a non-solvent for the polymer. The non-solvent is removed by critical point drying in CO.sub.2 at an elevated pressure and temperature or evaporation in a vacuum oven. The dried product is heated in an inert atmosphere in a first heating step to a first temperature and maintained there for a time sufficient to substantially cross-link the polymer material. The cross-linked polymer material is then carbonized in an inert atmosphere.

Hot and cold water as a supercritical solvent

NASA Astrophysics Data System (ADS)

Fuentevilla, Daphne Anne

This dissertation addresses the anomalous properties of water at high temperatures near the vapor-liquid critical point and at low temperatures in the supercooled liquid region. The first part of the dissertation is concerned with the concentration dependence of the critical temperature, density, and pressure of an aqueous sodium chloride solution. Because of the practical importance of an accurate knowledge of critical parameters for industrial, geochemical, and biological applications, an empirical equation for the critical locus of aqueous sodium chloride solutions was adopted in 1999 by the International Association for the Properties of Water and Steam (IAPWS) as a guideline. However, since this original Guideline on the Critical Locus of Aqueous Solutions of Sodium Chloride was developed, two new theoretical developments occurred, motivating the first part of this dissertation. Here, I present a theory-based formulation for the critical parameters of aqueous sodium chloride solutions as a proposed replacement for the empirical formulation currently in use. This formulation has been published in the International Journal of Thermophysics and recommended by the Executive Committee of IAPWS for adoption as a Revised Guideline on the Critical Locus of Aqueous Solutions of Sodium Chloride. The second part of the dissertation addresses a new concept, considering cold water as a supercritical solvent. Based on the idea of a second, liquid-liquid, critical point in supercooled water, we explore the possibility of supercooled water as a novel supercooled solvent through the thermodynamics of critical phenomena. In 2006, I published a Physical Review letter presenting a parametric scaled equation of state for supercooled-water. Further developments based on this work led to a phenomenological mean-field "two-state" model, clarifying the nature of the phase separation in a polyamorphic single-component liquid. In this dissertation, I modify this two-state model to incorporate solutes. Critical lines emanating from the pure-water critical point show how even small additions of solute may significantly affect the thermodynamic properties and phase behavior of supercooled aqueous solutions. Some solutes, such as glycerol, can prevent spontaneous crystallization, thus making liquid-liquid separation in supercooled water experimentally accessible. This work will help in resolving the question on liquid polyamorphism in supercooled water.

Towards a comprehensive model for the electronic and vibrational structure of the Creutz-Taube ion.

PubMed

Reimers, Jeffrey R; Wallace, Brett B; Hush, Noel S

2008-01-13

Since the synthesis of the Creutz-Taube ion, the nature of its charge localization has been of immense scientific interest, this molecule providing a model system for the understanding of the operation of biological photosynthetic and electron-transfer processes. However, recent work has shown that its nature remains an open question. Many systems of this type, including photosynthetic reaction centres, are of current research interest, and thereby the Creutz-Taube ion provides an important chemical paradigm: the key point of interest is the details of how such molecules behave. We lay the groundwork for the construction of a comprehensive model for its chemical and spectroscopic properties. Advances are described in some of the required areas including: simulation of electronic absorption spectra; quantitative depiction of the large interaction of the ion's electronic description with solvent motions; and the physics of Ru-NH3 spectator-mode vibrations. We show that details of the solvent electron-phonon coupling are critical in the interpretation of the spectator-mode vibrations, as these strongly mix with solvent motions when 0.75<2J/lambda<1. In this regime, a double-well potential exists which does not support localized zero-point vibration, and many observed properties of the Creutz-Taube ion are shown to be consistent with the hypothesis that the ion has this character.

Structure and diffusion of furans and other cellulose-derived compounds in solvents via MD simulation

NASA Astrophysics Data System (ADS)

Rabideau, Brooks; Ismail, Ahmed

2011-03-01

There is now a large push towards the development of energy sources that are both environmentally friendly and sustainable; with the conversion of cellulose derived from biomass into biofuels being one promising route. In this conversion, a variety of intermediary compounds have been identified, which appear critical to successful expansion of the process to an industrial scale. Here we examine the structure and diffusion of these furans and acids derived from cellulose within ionic liquids via molecular dynamic simulation. Ionic liquids have shown the ability to dissolve cellulose with certain `green' benefits over existing, conventional solvents. Specifically, we study the solvation properties of these chemicals by examining the pair correlation functions of solute with solvent, and by exploring the agglomeration and separation of these chemicals from the solvent as well as the hydrogen bonding between species. Additionally, we determine the diffusion constant of these compounds in ionic liquid and aqueous solvents.

The uncertainty of reference standards--a guide to understanding factors impacting uncertainty, uncertainty calculations, and vendor certifications.

PubMed

Gates, Kevin; Chang, Ning; Dilek, Isil; Jian, Huahua; Pogue, Sherri; Sreenivasan, Uma

2009-10-01

Certified solution standards are widely used in forensic toxicological, clinical/diagnostic, and environmental testing. Typically, these standards are purchased as ampouled solutions with a certified concentration. Vendors present concentration and uncertainty differently on their Certificates of Analysis. Understanding the factors that impact uncertainty and which factors have been considered in the vendor's assignment of uncertainty are critical to understanding the accuracy of the standard and the impact on testing results. Understanding these variables is also important for laboratories seeking to comply with ISO/IEC 17025 requirements and for those preparing reference solutions from neat materials at the bench. The impact of uncertainty associated with the neat material purity (including residual water, residual solvent, and inorganic content), mass measurement (weighing techniques), and solvent addition (solution density) on the overall uncertainty of the certified concentration is described along with uncertainty calculations.

Ultrahigh pressure extraction of bioactive compounds from plants-A review.

PubMed

Xi, Jun

2017-04-13

Extraction of bioactive compounds from plants is one of the most important research areas for pharmaceutical and food industries. Conventional extraction techniques are usually associated with longer extraction times, lower yields, more organic solvent consumption, and poor extraction efficiency. A novel extraction technique, ultrahigh pressure extraction, has been developed for the extraction of bioactive compounds from plants, in order to shorten the extraction time, decrease the solvent consumption, increase the extraction yields, and enhance the quality of extracts. The mild processing temperature of ultrahigh pressure extraction may lead to an enhanced extraction of thermolabile bioactive ingredients. A critical review is conducted to introduce the different aspects of ultrahigh pressure extraction of plants bioactive compounds, including principles and mechanisms, the important parameters influencing its performance, comparison of ultrahigh pressure extraction with other extraction techniques, advantages, and disadvantages. The future opportunities of ultrahigh pressure extraction are also discussed.

New Analytical Method for the Determination of Detergent Concentration in Water by Fabric Dyeing

ERIC Educational Resources Information Center

Seng, Set; Kita, Masakazu; Sugihara, Reiko

2007-01-01

The use of harmful organic solvents in classrooms has become a critical issue of concern in the field of chemistry education. This article describes a classroom activity at a high school in which an acrylic fabric was used as the extraction medium in the analysis of the detergent concentration in water instead of organic solvents. Dyes were used…

High throughput research and evaporation rate modeling for solvent screening for ethylcellulose barrier membranes in pharmaceutical applications.

PubMed

Schoener, Cody A; Curtis-Fisk, Jaime L; Rogers, True L; Tate, Michael P

2016-10-01

Ethylcellulose is commonly dissolved in a solvent or formed into an aqueous dispersion and sprayed onto various dosage forms to form a barrier membrane to provide controlled release in pharmaceutical formulations. Due to the variety of solvents utilized in the pharmaceutical industry and the importance solvent can play on film formation and film strength it is critical to understand how solvent can influence these parameters. To systematically study a variety of solvent blends and how these solvent blends influence ethylcellulose film formation, physical and mechanical film properties and solution properties such as clarity and viscosity. Using high throughput capabilities and evaporation rate modeling, thirty-one different solvent blends composed of ethanol, isopropanol, acetone, methanol, and/or water were formulated, analyzed for viscosity and clarity, and narrowed down to four solvent blends. Brookfield viscosity, film casting, mechanical film testing and water permeation were also completed. High throughput analysis identified isopropanol/water, ethanol, ethanol/water and methanol/acetone/water as solvent blends with unique clarity and viscosity values. Evaporation rate modeling further rank ordered these candidates from excellent to poor interaction with ethylcellulose. Isopropanol/water was identified as the most suitable solvent blend for ethylcellulose due to azeotrope formation during evaporation, which resulted in a solvent-rich phase allowing the ethylcellulose polymer chains to remain maximally extended during film formation. Consequently, the highest clarity and most ductile films were formed. Employing high throughput capabilities paired with evaporation rate modeling allowed strong predictions between solvent interaction with ethylcellulose and mechanical film properties.

The Use of Solar Heating and Heat Cured Polymers for Lunar Surface Stabilization

NASA Technical Reports Server (NTRS)

Hintze, Paul; Curran, Jerry; Back, Reddy

2008-01-01

Dust ejecta can affect visibility during a lunar landing, erode nearby coated surfaces and get into mechanical assemblies of in-place infrastructure. Regolith erosion was observed at many of the Apollo landing sites. This problem needs to be addressed at the beginning of the lunar base missions, as the amount of infrastructure susceptible to problems will increase with each landing. Protecting infrastructure from dust and debris is a crucial step in its long term functionality. A proposed way to mitigate these hazards is to build a lunar launch pad. Other areas of a lunar habitat will also need surface stabilization methods to help mitigate dust hazards. Roads would prevent dust from being lifted during movement and dust free zones might be required for certain areas critical to crew safety or to critical science missions. Work at NASA Kennedy Space Center (KSC) is investigating methods of stabilizing the lunar regolith including: sintering the regolith into a solid and using heat or UV cured polymers to stabilize the surface. Sintering, a method in which powders are heated until fusing into solids, has been proposed as one way of building a Lunar launch/landing pad. A solar concentrator has been built and used in the field to sinter JSC-1 Lunar stimulant. Polymer palliatives are used by the military to build helicopter landing pads and roads in dusty and sandy areas. Those polymers are dispersed in a solvent (water), making them unsuitable for lunar use. Commercially available, solvent free, polymer powders are being investigated to determine their viability to work in the same way as the solvent borne terrestrial analog. This presentation will describe the ongoing work at KSC in this field. Results from field testing will be presented. Physical testing results, including compression and abrasion, of field and laboratory prepared samples will be presented.

Bio-Oil Separation and Stabilization by Near-Critical Propane Fractionation

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

Ginosar, Daniel M.; Petkovic, Lucia M.; Agblevor, Foster A.

Bio-oils produced by thermal process are promising sources of sustainable, low greenhouse gas alternative fuels. These thermal processes are also well suited to decentralized energy production due to low capital and operating costs. Algae feedstocks for bio-oil production are of particular interest, due in part to their high-energy growth yields. Further, algae can be grown in non-arable areas in fresh, brackish, salt water, or even waste water. Unfortunately, bio-oils produced by thermal processes present significant stability challenges. These oils have complex chemical compositions, are viscous, reactive, and thermally unstable. Further, the components within the oils are difficult to separate bymore » fractional distillation. By far, the most effective separation and stabilization method has been solvent extraction. However, liquid phase extraction processes pose two main obstacles to commercialization; they require a significant amount of energy to remove and recover the solvent from the product, and they have a propensity for the solvent to become contaminated with minerals from the char and ash present in the original bio-oil. Separation and fractionation of thermally produced bio-oils using supercritical fluids (SCF) offers the advantages of liquid solvent extraction while drastically reducing energy demands and the predisposition to carry over solids into the extracted phase. SCFs are dense fluids with liquid-like solvent properties and gas-like transport properties. Further, SCF density and solvent strength can be tuned with minor adjustments in pressure, co-solvent addition, or gas anti-solvent addition. Catalytic pyrolysis oils were produced from Scenedesmus dimorphus algae using a fluid catalytic cracking catalyst. Bio-oil produced from catalytic fast pyrolysis (CFP) was separated using critical fluids. Propane extraction was performed at 65 °C at a fluid reduced pressure of 2.0 (85 bar) using an eight to one solvent to feed ratio by weight. Extraction of catalytic fast pyrolysis oil with near critical propane produced an oil extract that was physically and chemically different from and more stable than the original oil. The propane extract displayed lower viscosity and lower average molecular weight. The species present in the propane extract were likely the less polar that would be expected from using a non-polar solvent (propane). Carbonyl containing species in the extract were likely ketones and esters. The raffinate contained a higher amnount of OH bonded species along with the more polar more polar acids, amides, and alcohols. The higher concentration of nitrogen in the raffinate may confirm the presence of amides. Viscosity of the propane extract increased only half as much as that of the CFP bio-oil. Further, In situ NMR aging studies showed that the propane extract was more stable than the raw oil. In conclusion, propane extraction is a promising method to decrease the nitrogen content of bio-oils and to improve the stability of bio-oils obtained by the catalytic pyrolysis of algae based biomass.« less

Inhibition of gap junction currents by the abused solvent toluene.

PubMed

Del Re, Angelo M; Woodward, John J

2005-05-09

Abused inhalants are a large class of compounds that are inhaled for their intoxicating and mood altering effects. They include chemicals with known therapeutic uses such as anesthetic gases as well as volatile organic solvents like toluene that are found in paint thinners and adhesives. Because of their widespread commercial use and availability, inhalants are often among the first drugs that children encounter and use of these compounds is often associated with adverse acute and long-term consequences. The cellular and molecular sites of action for abused inhalants is not well known although recent studies report that toluene and other organic solvents alter the activity of specific ligand- and voltage-gated ion channels that regulate cellular excitability. As part of an ongoing effort to define molecular sites of action for abused inhalants, this study examined the effect of toluene on the function of gap junction proteins endogenously expressed in human embryonic kidney (HEK 293) cells. Gap junctions allow cell-to-cell electrical communication as well as passage of small molecular weight substances and are critical for synchronizing cellular activity in certain tissues. Gap junction currents in HEK 293 cells were measured during brief voltage steps using patch-clamp electrophysiology and were blocked by known gap junction blockers confirming expression of connexin proteins in these cells. Toluene dose-dependently inhibited these conductances with threshold effects appearing at approximately 0.4 mM and near complete inhibition occurring at concentrations of 1 mM and higher. The estimated EC50 value for toluene inhibition of gap junction currents in HEK 293 cells was 0.57 mM. The results of these studies suggest that volatile solvents including toluene may produce some of their effects by disrupting inter-cellular communication mediated by gap junction proteins.

Chemical Reactions in Supercritical Carbon Dioxide

NASA Astrophysics Data System (ADS)

Wai, Chien M.; Hunt, Fred; Ji, Min; Chen, Xiaoyuan

1998-12-01

Utilizing supercritical fluids as environmentally benign solvents for chemical synthesis is one of the new approaches in the "greening" of chemistry. Carbon dioxide is the most widely used gas for supercritical fluid studies because of its moderate critical constants, nontoxic nature, and availability in pure form. One unique property of supercritical carbon dioxide (sc-CO2) is its high solubility for fluorinated compounds. Thus sc-CO2 can be used to replace Freons that are conventionally used as solvents for synthesis of perfluoro-polymers. Another property of sc-CO2 is its miscibility with gases such as H2. Heterogeneous reactions involving these gases may become homogeneous reactions in sc-CO2. Reactions in sc-CO2 may offer several advantages including controlling phase behavior and products, increasing speed of reactions, and obtaining specific reaction channels. This paper describes the following nine types of chemical reactions reported in the literature utilizing sc-CO2 as a solvent to illustrate the unique properties of the supercritical fluid reaction systems: (i) hydrogenation and hydroformylation, (ii) synthesis of organometallic compounds, (iii) metal chelation and extraction, (iv) preparation of inorganic nanoparticles, (v) stereo-selectivity of lipase-catalyzed reactions, (vi) asymmetric catalytic hydrogenation, (vii) polymerization, (viii) Diels-Alder reaction, and (ix) free radical reactions.

Precision Cleaning and Verification Processes Used at Marshall Space Flight Center for Critical Hardware Applications

NASA Technical Reports Server (NTRS)

Caruso, Salvadore V.; Cox, Jack A.; McGee, Kathleen A.

1998-01-01

Marshall Space Flight Center (MSFC) of the National Aeronautics and Space Administration performs many research and development programs that require hardware and assemblies to be cleaned to levels that are compatible with fuels and oxidizers (liquid oxygen, solid propellants, etc.). Also, MSFC is responsible for developing large telescope satellites which require a variety of optical systems to be cleaned. A precision cleaning shop is operated within MSFC by the Fabrication Services Division of the Materials & Processes Laboratory. Verification of cleanliness is performed for all precision cleaned articles in the Environmental and Analytical Chemistry Branch. Since the Montreal Protocol was instituted, MSFC had to find substitutes for many materials that have been in use for many years, including cleaning agents and organic solvents. As MSFC is a research center, there is a great variety of hardware that is processed in the Precision Cleaning Shop. This entails the use of many different chemicals and solvents, depending on the nature and configuration of the hardware and softgoods being cleaned. A review of the manufacturing cleaning and verification processes, cleaning materials and solvents used at MSFC and changes that resulted from the Montreal Protocol will be presented.

Precision Cleaning and Verification Processes Used at Marshall Space Flight Center for Critical Hardware Applications

NASA Technical Reports Server (NTRS)

Caruso, Salvadore V.

1999-01-01

Marshall Space Flight Center (MSFC) of the National Aeronautics and Space Administration (NASA) performs many research and development programs that require hardware and assemblies to be cleaned to levels that are compatible with fuels and oxidizers (liquid oxygen, solid propellants, etc.). Also, the Center is responsible for developing large telescope satellites which requires a variety of optical systems to be cleaned. A precision cleaning shop is operated with-in MSFC by the Fabrication Services Division of the Materials & Processes Division. Verification of cleanliness is performed for all precision cleaned articles in the Analytical Chemistry Branch. Since the Montreal Protocol was instituted, MSFC had to find substitutes for many materials that has been in use for many years, including cleaning agents and organic solvents. As MSFC is a research Center, there is a great variety of hardware that is processed in the Precision Cleaning Shop. This entails the use of many different chemicals and solvents, depending on the nature and configuration of the hardware and softgoods being cleaned. A review of the manufacturing cleaning and verification processes, cleaning materials and solvents used at MSFC and changes that resulted from the Montreal Protocol will be presented.

Critical Surface Cleaning and Verification Alternatives

NASA Technical Reports Server (NTRS)

Melton, Donald M.; McCool, A. (Technical Monitor)

2000-01-01

As a result of federal and state requirements, historical critical cleaning and verification solvents such as Freon 113, Freon TMC, and Trichloroethylene (TCE) are either highly regulated or no longer 0 C available. Interim replacements such as HCFC 225 have been qualified, however toxicity and future phase-out regulations necessitate long term solutions. The scope of this project was to qualify a safe and environmentally compliant LOX surface verification alternative to Freon 113, TCE and HCFC 225. The main effort was focused on initiating the evaluation and qualification of HCFC 225G as an alternate LOX verification solvent. The project was scoped in FY 99/00 to perform LOX compatibility, cleaning efficiency and qualification on flight hardware.

Organic Solvent Effects in Biomass Conversion Reactions.

PubMed

Shuai, Li; Luterbacher, Jeremy

2016-01-01

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

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.

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

Mathias, Paul M.; Afshar, Kash; Zheng, Feng

This paper describes an unusual solvent regeneration method unique to CO₂BOLs and other switchable ionic liquids; utilizing changes in polarity to shift the free energy of the system. The degree of CO₂ loading in CO₂BOLs is known to control the polarity of the solvent; conversely, polarity could be exploited as a means to control CO₂ loading. In this process, a chemically inert non-polar “antisolvent” is added to aid in de-complexing CO₂ from a CO₂-rich CO₂BOL. The addition of this polarity assist reduces temperatures required for regeneration of CO₂BOLs by as much as 76 °C. The lower regeneration temperatures realized withmore » this polarity change allow for reduced solvent attrition and thermal degradation. Furthermore, the polarity assist shows considerable promise for reducing regeneration energy of CO₂BOL solvents, and separation of the CO₂BOL from the antisolvent is as simple as cooling the mixture below the upper critical solution temperature. Vapour-liquid equilibrium and liquid-liquid equilibrium measurements of a candidate CO₂BOL with CO₂ with and without an antisolvent were completed. From this data, we present the evidence and impacts of a polarity change on a CO₂BOL. Thermodynamic models and analysis of the system were constructed using ASPEN Plus, and forecasts preliminary process configurations and feasibility are also presented. Lastly, projections of solvent performance for removing CO₂ from a sub-critical coal fired power plant (total net power and parasitic load) are presented with and without this polarity assist and compared to DOE’s Case 10 MEA baseline.« less

A Physicochemical Method for Separating Rare Earths: Addressing an Impending Shortfall

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

Schelter, Eric

2017-03-14

There are currently zero operating suppliers of critical rare earth elements La–Lu, Sc, Y (REs), in the western hemisphere. REs are critical materials due to their importance in clean energy and defense applications, including permanent magnets in wind turbines and phosphors in energy efficient lighting. It is not economically viable to produce pure REs in the U.S. given current separations technology. REs production is dominated by suppliers in the People’s Republic of China (PRC) because of their capacity in liquid­liquid solvent extraction (SX) used to purify mixtures. Weak environmental regulations in the PRC also contribute to a competitive advantage. SXmore » is a cost, time, solvent and waste intensive process but is highly optimized and scalable. The low efficiency of SX derives from the small thermodynamic differences in solvation enthalpy between the RE3+ cations. To foster stable domestic RE production there is a critical need for fundamentally new REs chemistry that contributes to disruptive technologies in RE separations. The overall goal of this project was to develop new thermodynamic bases, and apply them, for the solution separation of rare earth metals. We have developed the chemistry of rare earth metals: La–Lu, Sc and Y, with redox active ligands. Our hypothesis for the project was that electron­hole coupling in complexes of certain lanthanide metals with redox active ligands can be used to manifest chemical distinctiveness and affect separations. We also developed separations based on unique solution equilibria from tailored ligands.« less

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

DOEpatents

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

2009-01-06

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

Method for the preparation of high surface area high permeability carbons

DOEpatents

Lagasse, R.R.; Schroeder, J.L.

1999-05-11

A method for preparing carbon materials having high surface area and high macropore volume to provide high permeability. These carbon materials are prepared by dissolving a carbonizable polymer precursor, in a solvent. The solution is cooled to form a gel. The solvent is extracted from the gel by employing a non-solvent for the polymer. The non-solvent is removed by critical point drying in CO{sub 2} at an elevated pressure and temperature or evaporation in a vacuum oven. The dried product is heated in an inert atmosphere in a first heating step to a first temperature and maintained there for a time sufficient to substantially cross-link the polymer material. The cross-linked polymer material is then carbonized in an inert atmosphere. 3 figs.

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

PubMed

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

2009-05-13

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

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.

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.

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

PubMed

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

2017-08-18

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

Chemically assisted mechanical refrigeration process

DOEpatents

Vobach, Arnold R.

1987-01-01

There is provided a chemically assisted mechanical refrigeration process including the steps of: mechanically compressing a refrigerant stream which includes vaporized refrigerant; contacting the refrigerant with a solvent in a mixer (11) at a pressure sufficient to promote substantial dissolving of the refrigerant in the solvent in the mixer (11) to form a refrigerant-solvent solution while concurrently placing the solution in heat exchange relation with a working medium to transfer energy to the working medium, said refrigerant-solvent solution exhibiting a negative deviation from Raoult's Law; reducing the pressure over the refrigerant-solvent solution in an evaporator (10) to allow the refrigerant to vaporize and substantially separate from the solvent while concurrently placing the evolving refrigerant-solvent solution in heat exchange relation with a working medium to remove energy from the working medium to thereby form a refrigerant stream and a solvent stream; and passing the solvent and refrigerant stream from the evaporator.

Chemically assisted mechanical refrigeration process

DOEpatents

Vobach, Arnold R.

1987-01-01

There is provided a chemically assisted mechanical refrigeration process including the steps of: mechanically compressing a refrigerant stream which includes vaporized refrigerant; contacting the refrigerant with a solvent in a mixer (11) at a pressure sufficient to promote substantial dissolving of the refrigerant in the solvent in the mixer (11) to form a refrigerant-solvent solution while concurrently placing the solution in heat exchange relation with a working medium to transfer energy to the working medium, said refrigerant-solvent solution exhibiting a negative deviation from Raoult's Law; reducing the pressure over the refrigerant-solvent solution in an evaporator (10) to allow the refrigerant to vaporize and substantially separate from the solvent while concurrently placing he evolving refrigerant-solvent solution in heat exchange relation with a working medium to remove energy from the working medium to thereby form a refrigerant stream and a solvent stream; and passing the solvent and refrigerant stream from the evaporator.

Chemically assisted mechanical refrigeration process

DOEpatents

Vobach, A.R.

1987-06-23

There is provided a chemically assisted mechanical refrigeration process including the steps of: mechanically compressing a refrigerant stream which includes vaporized refrigerant; contacting the refrigerant with a solvent in a mixer at a pressure sufficient to promote substantial dissolving of the refrigerant in the solvent in the mixer to form a refrigerant-solvent solution while concurrently placing the solution in heat exchange relation with a working medium to transfer energy to the working medium, said refrigerant-solvent solution exhibiting a negative deviation from Raoult's Law; reducing the pressure over the refrigerant-solvent solution in an evaporator to allow the refrigerant to vaporize and substantially separate from the solvent while concurrently placing the evolving refrigerant-solvent solution in heat exchange relation with a working medium to remove energy from the working medium to thereby form a refrigerant stream and a solvent stream; and passing the solvent and refrigerant stream from the evaporator. 5 figs.

Chemically assisted mechanical refrigeration process

DOEpatents

Vobach, A.R.

1987-11-24

There is provided a chemically assisted mechanical refrigeration process including the steps of: mechanically compressing a refrigerant stream which includes vaporized refrigerant; contacting the refrigerant with a solvent in a mixer at a pressure sufficient to promote substantial dissolving of the refrigerant in the solvent in the mixer to form a refrigerant-solvent solution while concurrently placing the solution in heat exchange relation with a working medium to transfer energy to the working medium, said refrigerant-solvent solution exhibiting a negative deviation from Raoult's Law; reducing the pressure over the refrigerant-solvent solution in an evaporator to allow the refrigerant to vaporize and substantially separate from the solvent while concurrently placing the evolving refrigerant-solvent solution in heat exchange relation with a working medium to remove energy from the working medium to thereby form a refrigerant stream and a solvent stream; and passing the solvent and refrigerant stream from the evaporator. 5 figs.

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

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.

Optimization of Preparation Techniques for Poly(Lactic Acid-Co-Glycolic Acid) Nanoparticles

NASA Astrophysics Data System (ADS)

Birnbaum, Duane T.; Kosmala, Jacqueline D.; Brannon-Peppas, Lisa

2000-06-01

Microparticles and nanoparticles of poly(lactic acid-co-glycolic acid) (PLAGA) are excellent candidates for the controlled release of many pharmaceutical compounds because of their biodegradable nature. The preparation of submicron PLAGA particles poses serious challenges that are not necessarily present when preparing microparticles. We have evaluated several combinations of organic solvents and surfactants used in the formulation of PLAGA nanoparticles. Critical factors such as the ability to separate the nanoparticles from the surfactant, the ability to re-suspend the nanoparticles after freeze-drying, formulation yield and nanoparticle size were studied. The smallest particles were obtained using the surfactant/solvent combination of sodium dodecyl sulfate and ethyl acetate (65 nm) and the largest particles were obtained using poly(vinyl alcohol) and dichloromethane (466 nm). However, the optimal nanoparticles were produced using either acetone or ethyl acetate as the organic solvent and poly(vinyl alcohol) or human serum albumin as the surfactant. This is because the most critical measure of performance of these nanoparticles proved to be their ability to re-suspend after freeze-drying.

Optimized Solvent for Energy-Efficient, Environmentally-Friendly Capture of CO{sub 2} at Coal-Fired Power Plants

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

Farthing, G. A.; Rimpf, L. M.

The overall goal of this project, as originally proposed, was to optimize the formulation of a novel solvent as a critical enabler for the cost-effective, energy-efficient, environmentally-friendly capture of CO{sub 2} at coal-fired utility plants. Aqueous blends of concentrated piperazine (PZ) with other compounds had been shown to exhibit high rates of CO{sub 2} absorption, low regeneration energy, and other desirable performance characteristics during an earlier 5-year development program conducted by B&W. The specific objective of this project was to identify PZ-based solvent formulations that globally optimize the performance of coal-fired power plants equipped with CO{sub 2} scrubbing systems. Whilemore » previous solvent development studies have tended to focus on energy consumption and absorber size, important issues to be sure, the current work seeks to explore, understand, and optimize solvent formulation across the full gamut of issues related to commercial application of the technology: capital and operating costs, operability, reliability, environmental, health and safety (EH&S), etc. Work on the project was intended to be performed under four budget periods. The objective of the work in the first budget period has been to identify several candidate formulations of a concentrated PZ-based solvent for detailed characterization and evaluation. Work in the second budget period would generate reliable and comprehensive property and performance data for the identified formulations. Work in the third budget period would quantify the expected performance of the selected formulations in a commercial CO{sub 2} scrubbing process. Finally, work in the fourth budget period would provide a final technology feasibility study and a preliminary technology EH&S assessment. Due to other business priorities, however, B&W has requested that this project be terminated at the end of the first budget period. This document therefore serves as the final report for this project. It is the first volume of the two-volume final report and summarizes Budget Period 1 accomplishments under Tasks 1-5 of the project, including the selection of four solvent formulations for further study.« less

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.

Micron-sized columnar grains of CH3NH3PbI3 grown by solvent-vapor assisted low-temperature (75 °C) solid-state reaction: The role of non-coordinating solvent-vapor

NASA Astrophysics Data System (ADS)

Zheng, Huifeng; Liu, Yangqiao; Sun, Jing

2018-04-01

The preparation of hybrid perovskite films with large columnar grains via low-temperature solid-state reaction remains a big challenge. Conventional solvent annealing using DMF, DMSO and ethanol, etc. fails to work effectively at low temperature (<100 °C). Here, we comprehensively investigated the effects of non-coordinating solvent vapor on the properties of perovskite film, and obtained micron-sized columnar grains (with an average grain size of 1.4 μm) of CH3NH3PbI3 even at a low temperature of 75 °C when annealed with benzyl alcohol vapor. The perovskite solar cells based on benzyl-alcohol-vapor annealing (75 °C), delivered much higher photovoltaic performance, better stability and smaller hysteresis than those based on conventional thermal annealing. Additionally, a champion power conversion efficiency (PCE) of 15.1% was obtained and the average PCE reached 12.2% with a tiny deviation. Finally, the mechanism of solvent annealing with non-coordinating solvent was discussed. Moreover, we revealed that high polarity and high boiling point of the solvent used for generating vapor, was critical to grow micron-sized columnar grains at such a low temperature (75 °C). This work will contribute to understanding the mechanism of grain growth in solvent annealing and improving its facility and effectiveness.

Long-range single domain array of a 5 nm pattern of supramolecules via solvent annealing in a double-sandwich cell.

PubMed

Kwon, Kiok; Park, Kangho; Jung, Hee-Tae

2018-05-10

In nanotechnology and microelectronics research, the generation of an ultradense, single-grain nanostructure with a long-range lateral order is challenging. In this paper, we report upon a new solvent-annealing method using a double-sandwich confinement to promote the formation of a large-area, single-domain array (>0.3 × 0.3 mm2) of supramolecular cylinders with a small feature size (4.7 nm). The in situ GISAXS experiment result shows the ordering process during solvent evaporation. The diffusion of the solvent molecules led to the disassembly of the supramolecules confined between the top and bottom surfaces and their subsequent mobilization, thereby producing a highly ordered hexagonal array of supramolecular materials under the double-sandwich confinement upon solvent evaporation. In addition, two key factors were found to be crucial in this process for generating highly-ordered supramolecular building blocks: (i) the presence of a top coat during solvent evaporation to provide a geometric confinement template, and (ii) the control of the solvent evaporation rate during the solvent evaporation step to provide the dendrimer sufficient time to self-assemble into the highly ordered state over a large area. Our developed approach, which can be extended to be used for a large family of supramolecules, is of critical importance in providing a new bottom-up lithographic method based on supramolecular self-assembly.

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.

Investigating the potential of electrospun gelatin and collagen scaffolds for tissue engineering applications

NASA Astrophysics Data System (ADS)

Sisson, Kristin M.

Electrospinning provides an avenue to explore tissue engineering with the ability to produce nano- and micro-sized fibers in a non-woven construct with properties ideal for a tissue engineered scaffold including: small diameter fibers, which create a large surface to volume ratio, and an interconnected porous network that enables cell migration, good mechanical integrity and a three-dimensional structure. A tissue engineered scaffold also must be biocompatible, biodegradable, non-toxic and able to be sterilized. All of these requirements can be satisfied by choosing an appropriate polymer and solvent system for electrospinning. The main objective of this research is to create a non-toxic, flat, bone tissue engineered scaffold to place into a non-immune compromised mouse. The current bone tissue repair and replacement methodologies include using metal and ceramic replacements or autologous and autogenous bone grafts. Each of these has its own set of disadvantages. Autologous grafts are bone harvested in one location in a patient and used in another location. This procedure is expensive, often results in pain and infection at the replacement site, and the actual harvesting procedure can cause problems for the patient. Autogenous grafts are bone harvested in one patient and used in another patient. The shortcomings include low donor availability and the possibility of rejection of the implant. The other options include using metal and ceramics to create replacement bone. However, metals provide good mechanical stability but can fail due to infection and also have poor integration into natural tissue. Ceramics, on the other hand, are brittle and have very low tensile strength. The natural extracellular matrix (ECM) of bone consists mainly of collagen type I. Electrospun fiber diameters closely resemble those of the natural ECM of bone. Thus, electrospinning a natural polymer like collagen type I for bone tissue engineering could make sense. Applications for these electrospun tissue engineered scaffolds include flat bone repair (skull, scapula, pelvis and sternum) or replacement applications. In order to meet the main objective, several critical milestones must be completed. The first is to develop an electrospinning system that uses less toxic solvents. Until recently, fluorinated solvents have been used to electrospin collagen and gelatin. These fluorinated solvents are cytotoxic and, even with vacuum drying and extensive washing, these toxic solvents may remain in the electrospun scaffolds. A solvent system using less toxic, non-fluorinated solvents to electrospin collagen and gelatin is necessary. Due to the high expense of collagen type I, gelatin is being used as a material substitute since gelatin is simply denatured collagen. Gelatin, like collagen, will dissolve in aqueous media unless it is crosslinked. The chemical generally used for crosslinking gelatin is glutaraldehyde, which is considered toxic. Therefore, the second objective is to find a less toxic method to crosslink the electrospun gelatin while maintaining the fiber morphology. The new crosslinking methods must also prove to be biocompatible in vivo. Another important objective is to investigate cell penetration as a function of fiber size, which is directly proportional to pore size. The final objective involves growing bone cells such as MG63 (osteoblast-like) in the electrospun scaffolds and compare to two-dimensional culture.

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

DOEpatents

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

2009-01-06

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

Microencapsulation Processes

NASA Astrophysics Data System (ADS)

Whateley, T. L.; Poncelet, D.

2005-06-01

Microencapsulation by solvent evaporation is a novel technique to enable the controlled delivery of active materials.The controlled release of drugs, for example, is a key challenge in the pharmaceutical industries. Although proposed several decades ago, it remains largely an empirical laboratory process.The Topical Team has considered its critical points and the work required to produce a more effective technology - better control of the process for industrial production, understanding of the interfacial dynamics, determination of the solvent evaporation profile, and establishment of the relation between polymer/microcapsule structures.The Team has also defined how microgravity experiments could help in better understanding microencapsulation by solvent evaporation, and it has proposed a strategy for a collaborative project on the topic.

Contamination of Critical Surfaces from NVR Glove Residues Via Dry Handling and Solvent Cleaning

NASA Technical Reports Server (NTRS)

Sovinski, Marjorie F.

2004-01-01

Gloves are often used to prevent the contamination of critical surfaces during handling. The type of glove chosen for use should be the glove that produces the least amount of non-volatile residue (NVR). This paper covers the analysis of polyethylene, nitrile, latex, vinyl, and polyurethane gloves using the contact transfer and gravimetric determination methods covered in the NASA GSFC work instruction Gravimetric Determination and Contact Transfer of Non-volatile Residue (NVR) in Cleanroom Glove Samples, 541-WI-5330.1.21 and in the ASTM Standard E-1731M-95, Standard Test Method for Gravimetric Determination of Non-Volatile Residue from Cleanroom Gloves. The tests performed focus on contamination of critical surfaces at the molecular level. The study found that for the most part, all of the gloves performed equally well in the contact transfer testing. However, the polyethylene gloves performed the best in the gravimetric determination testing, and therefore should be used whenever solvent contact is a possibility. The nitrile gloves may be used as a substitute for latex gloves when latex sensitivity is an issue. The use of vinyl gloves should be avoided, especially if solvent contact is a possibility. A glove database will be established by Goddard Space Flight Center (GSFC) Code 541 to compile the results from future testing of new gloves and different glove lots.

Electrolyte Suitable for Use in a Lithium Ion Cell or Battery

NASA Technical Reports Server (NTRS)

McDonald, Robert C. (Inventor)

2014-01-01

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

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

Electrolytes including fluorinated solvents for use in electrochemical cells

DOEpatents

Tikhonov, Konstantin; Yip, Ka Ki; Lin, Tzu-Yuan

2015-07-07

Provided are electrochemical cells and electrolytes used to build such cells. The electrolytes include ion-supplying salts and fluorinated solvents capable of maintaining single phase solutions with the salts at between about -30.degree. C. to about 80.degree. C. The fluorinated solvents, such as fluorinated carbonates, fluorinated esters, and fluorinated esters, are less flammable than their non-fluorinated counterparts and increase safety characteristics of cells containing these solvents. The amount of fluorinated solvents in electrolytes may be between about 30% and 80% by weight not accounting weight of the salts. Fluorinated salts, such as fluoroalkyl-substituted LiPF.sub.6, fluoroalkyl-substituted LiBF.sub.4 salts, linear and cyclic imide salts as well as methide salts including fluorinated alkyl groups, may be used due to their solubility in the fluorinated solvents. In some embodiments, the electrolyte may also include a flame retardant, such as a phosphazene or, more specifically, a cyclic phosphazene and/or one or more ionic liquids.

RETRACTED: Neoteric FT-IR investigation on the functional groups of phosphonium-based deep eutectic solvents.

PubMed

Aissaoui, Tayeb; AlNashef, Inas M; Hayyan, Maan; Hashim, Mohd Ali

2015-10-05

Deep eutectic solvents (DESs) are novel solvent media that are currently under investigation as an alternative to ionic liquids and conventional solvents. The physical properties of DESs as well as their mild environmental footprint and potentially critical industrial application necessitate understanding the interaction of functional groups on both the salt and hydrogen bond donor (HBD). In this study, four DESs were prepared by mixing triethylenglycol, diethylenglycol, ethylenglycol, and glycerol as HBDs with methyltriphenylphosphonium bromide as a salt at a molar ratio of 1:4. Fourier transform infrared spectroscopy was conducted to highlight the chemical structure and mechanism of the combination of the four DESs. New spectra illustrating the combination of the functional groups of the HBDs and salt were observed and interpreted. This study is the first to investigate the properties of neoteric phosphonium-based DESs. Copyright © 2015 Elsevier B.V. All rights reserved.

Balancing size exclusion and adsorption of polymers in nanopores

NASA Astrophysics Data System (ADS)

Kim, Won; Ryu, Chang Y.

2006-03-01

The liquid chromatography at critical condition (LCCC) presents the condition, at which the size exclusion and adsorption of polymer chains are balanced upon interactions with nanoporous substrates. In this study, we investigate how the polymer interactions with nanopores are affected by the solvent quality and nanopore size. Specifically, we measure the retention times of monodisperse polystyrenes in C18-bonded nanoporous silica column as a function of molecular weight, when a mixed solvent of methylene chloride and acetonitrile are used as elutent. C18-bonded silica particles with 70, 100, and 250 A pore size are used as a stationary phase to study how the transition from SEC-like to IC-like retention behavior depends on the condition of temperature and solvent composition. To locate the LCCC at various nanopore sizes, the temperature and solvent composition have been varied from 0 to 60 C and from 51 to 62 v/v% of methylene chloride, respectively.

An adaptive quantum mechanics/molecular mechanics method for the infrared spectrum of water: incorporation of the quantum effect between solute and solvent.

PubMed

Watanabe, Hiroshi C; Banno, Misa; Sakurai, Minoru

2016-03-14

Quantum effects in solute-solvent interactions, such as the many-body effect and the dipole-induced dipole, are known to be critical factors influencing the infrared spectra of species in the liquid phase. For accurate spectrum evaluation, the surrounding solvent molecules, in addition to the solute of interest, should be treated using a quantum mechanical method. However, conventional quantum mechanics/molecular mechanics (QM/MM) methods cannot handle free QM solvent molecules during molecular dynamics (MD) simulation because of the diffusion problem. To deal with this problem, we have previously proposed an adaptive QM/MM "size-consistent multipartitioning (SCMP) method". In the present study, as the first application of the SCMP method, we demonstrate the reproduction of the infrared spectrum of liquid-phase water, and evaluate the quantum effect in comparison with conventional QM/MM simulations.

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).

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

NASA Astrophysics Data System (ADS)

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

2018-01-01

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

Conformation of ionizable poly Para phenylene ethynylene in dilute solutions

DOE PAGES

Wijesinghe, Sidath; Maskey, Sabina; Perahia, Dvora; ...

2015-11-03

The conformation of dinonyl poly para phenylene ethynylenes (PPEs) with carboxylate side chains, equilibrated in solvents of different quality is studied using molecular dynamics simulations. PPEs are of interest because of their tunable electro-optical properties, chemical diversity, and functionality which are essential in wide range of applications. The polymer conformation determines the conjugation length and their assembly mode and affects electro-optical properties which are critical in their current and potential uses. The current study investigates the effect of carboxylate fraction on PPEs side chains on the conformation of chains in the dilute limit, in solvents of different quality. The dinonylmore » PPE chains are modeled atomistically, where the solvents are modeled both implicitly and explicitly. Dinonyl PPEs maintained a stretched out conformation up to a carboxylate fraction f of 0.7 in all solvents studied. The nonyl side chains are extended and oriented away from the PPE backbone in toluene and in implicit good solvent whereas in water and implicit poor solvent, the nonyl side chains are collapsed towards the PPE backbone. Thus, rotation around the aromatic ring is fast and no long range correlations are seen within the backbone.« less

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

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

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

2017-03-19

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

Conformation of ionizable poly Para phenylene ethynylene in dilute solutions

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

Wijesinghe, Sidath; Maskey, Sabina; Perahia, Dvora

The conformation of dinonyl poly para phenylene ethynylenes (PPEs) with carboxylate side chains, equilibrated in solvents of different quality is studied using molecular dynamics simulations. PPEs are of interest because of their tunable electro-optical properties, chemical diversity, and functionality which are essential in wide range of applications. The polymer conformation determines the conjugation length and their assembly mode and affects electro-optical properties which are critical in their current and potential uses. The current study investigates the effect of carboxylate fraction on PPEs side chains on the conformation of chains in the dilute limit, in solvents of different quality. The dinonylmore » PPE chains are modeled atomistically, where the solvents are modeled both implicitly and explicitly. Dinonyl PPEs maintained a stretched out conformation up to a carboxylate fraction f of 0.7 in all solvents studied. The nonyl side chains are extended and oriented away from the PPE backbone in toluene and in implicit good solvent whereas in water and implicit poor solvent, the nonyl side chains are collapsed towards the PPE backbone. Thus, rotation around the aromatic ring is fast and no long range correlations are seen within the backbone.« less

Process for producing low-sulfur boiler fuel by hydrotreatment of solvent deashed SRC

DOEpatents

Roberts, George W.; Tao, John C.

1985-01-01

In this invention, a process is disclosed characterized by heating a slurry of coal in the presence of a process-derived recycle solvent and passing same to a dissolver zone, separating the resultant gases and liquid/solid products therefrom, vacuum distilling the liquid/solids products, separating the portions of the liquid/solids vacuum distillation effluent into a solid ash, unconverted coal particles and SRC material having a boiling point above 850.degree. F. and subjecting same to a critical solvent deashing step to provide an ash-free SRC product. The lighter liquid products from the vacuum distillation possess a boiling point below 850.degree. F. and are passed through a distillation tower, from which recycled solvent is recovered in addition to light distillate boiling below 400.degree. F. (overhead). The ash-free SRC product in accompanyment with at least a portion of the process derived solvent is passed in combination to a hydrotreating zone containing a hydrogenation catalyst and in the presence of hydrogen is hydroprocessed to produce a desulfurized and denitrogenized low-sulfur, low-ash boiler fuel and a process derived recycle solvent which is recycled to slurry the coal in the beginning of the process before heating.

CONTROL MEANS FOR A NUCLEAR REACTOR

DOEpatents

Teitel, R.J.

1961-09-01

A control means is described for a reactor which employs a liquid fuel consisting of a fissile isotope in a liquid bismuth solvent. The liquid fuel is contained in a plurality of tubular vessels. Control is effected by inserting plungers in the vessels to displace the liquid fuel and provide a critical or non- critical fuel configuration as desired.

Solvent wash solution

DOEpatents

Neace, J.C.

1984-03-13

A process is claimed for removing diluent degradation products from a solvent extraction solution, which has been used to recover uranium and plutonium from spent nuclear fuel. A wash solution and the solvent extraction solution are combined. The wash solution contains (a) water and (b) up to about, and including, 50 vol % of at least one-polar water-miscible organic solvent based on the total volume of the water and the highly-polar organic solvent. The wash solution also preferably contains at least one inorganic salt. The diluent degradation products dissolve in the highly-polar organic solvent and the organic solvent extraction solvent do not dissolve in the highly-polar organic solvent. The highly-polar organic solvent and the extraction solvent are separated.

Solvent wash solution

DOEpatents

Neace, James C.

1986-01-01

Process for removing diluent degradation products from a solvent extraction solution, which has been used to recover uranium and plutonium from spent nuclear fuel. A wash solution and the solvent extraction solution are combined. The wash solution contains (a) water and (b) up to about, and including, 50 volume percent of at least one-polar water-miscible organic solvent based on the total volume of the water and the highly-polar organic solvent. The wash solution also preferably contains at least one inorganic salt. The diluent degradation products dissolve in the highly-polar organic solvent and the organic solvent extraction solvent do not dissolve in the highly-polar organic solvent. The highly-polar organic solvent and the extraction solvent are separated.

Electric current-producing device having sulfone-based electrolyte

DOEpatents

Angell, Charles Austen; Sun, Xiao-Guang

2010-11-16

Electrolytic solvents and applications of such solvents including electric current-producing devices. For example, a solvent can include a sulfone compound of R1--SO2--R2, with R1 being an alkyl group and R2 a partially oxygenated alkyl group, to exhibit high chemical and thermal stability and high oxidation resistance. For another example, a battery can include, between an anode and a cathode, an electrolyte which includes ionic electrolyte salts and a non-aqueous electrolyte solvent which includes a non-symmetrical, non-cyclic sulfone. The sulfone has a formula of R1--SO2--R2, wherein R1 is a linear or branched alkyl or partially or fully fluorinated linear or branched alkyl group having 1 to 7 carbon atoms, and R2 is a linear or branched or partially or fully fluorinated linear or branched oxygen containing alkyl group having 1 to 7 carbon atoms. The electrolyte can include an electrolyte co-solvent and an electrolyte additive for protective layer formation.

Advanced separators based on aromatic polymer for high energy density lithium batteries

DOEpatents

Zhang, Zhengcheng; Woo, Jung-Je; Amine, Khalil

2017-03-21

A process includes casting a solution including poly(phenylene oxide), inorganic nanoparticles, a solvent, and a non-solvent on a substrate; and removing the solvent to form a porous film; wherein: the porous film is configured for use as a porous separator for a lithium ion battery.

Composites

NASA Astrophysics Data System (ADS)

Taylor, John G.

The Composites market is arguably the most challenging and profitable market for phenolic resins aside from electronics. The variety of products and processes encountered creates the challenges, and the demand for high performance in critical operations brings value. Phenolic composite materials are rendered into a wide range of components to supply a diverse and fragmented commercial base that includes customers in aerospace (Space Shuttle), aircraft (interiors and brakes), mass transit (interiors), defense (blast protection), marine, mine ducting, off-shore (ducts and grating) and infrastructure (architectural) to name a few. For example, phenolic resin is a critical adhesive in the manufacture of honeycomb sandwich panels. Various solvent and water based resins are described along with resin characteristics and the role of metal ions for enhanced thermal stability of the resin used to coat the honeycomb. Featured new developments include pultrusion of phenolic grating, success in RTM/VARTM fabricated parts, new ballistic developments for military vehicles and high char yield carbon-carbon composites along with many others. Additionally, global regional market resin volumes and sales are presented and compared with other thermosetting resin systems.

Changing the Mechanism for CO 2 Hydrogenation Using Solvent-Dependent Thermodynamics

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

Burgess, Samantha A.; Appel, Aaron M.; Linehan, John C.

A critical scientific challenge for utilization of CO2 is the development of catalyst systems that do not depend upon expensive or environmentally unfriendly reagents, such as precious metals, strong organic bases, and organic solvents. We have used thermodynamic insights to predict and demonstrate that the HCoI(dmpe)2 catalyst system, previously described for use in organic solvents, can hydrogenate CO2 to formate in water with bicarbonate as the only added reagent. Replacing tetrahydrofuran as the solvent with water changes the mechanism for catalysis by altering the thermodynamics for hydride transfer to CO2 from a key dihydride intermediate. The need for a strongmore » organic base was eliminated by performing catalysis in water due to the change in mechanism. These studies demonstrate that the solvent plays a pivotal role in determining the reaction thermodynamics and thereby catalytic mechanism and activity. The research was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences. Pacific Northwest National Laboratory is operated by Battelle for the U.S. Department of Energy.« less

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

Solvent-Assisted Gel Printing for Micropatterning Thin Organic-Inorganic Hybrid Perovskite Films.

PubMed

Jeong, Beomjin; Hwang, Ihn; Cho, Sung Hwan; Kim, Eui Hyuk; Cha, Soonyoung; Lee, Jinseong; Kang, Han Sol; Cho, Suk Man; Choi, Hyunyong; Park, Cheolmin

2016-09-27

While tremendous efforts have been made for developing thin perovskite films suitable for a variety of potential photoelectric applications such as solar cells, field-effect transistors, and photodetectors, only a few works focus on the micropatterning of a perovskite film which is one of the most critical issues for large area and uniform microarrays of perovskite-based devices. Here we demonstrate a simple but robust method of micropatterning a thin perovskite film with controlled crystalline structure which guarantees to preserve its intrinsic photoelectric properties. A variety of micropatterns of a perovskite film are fabricated by either microimprinting or transfer-printing a thin spin-coated precursor film in soft-gel state with a topographically prepatterned elastomeric poly(dimethylsiloxane) (PDMS) mold, followed by thermal treatment for complete conversion of the precursor film to a perovskite one. The key materials development of our solvent-assisted gel printing is to prepare a thin precursor film with a high-boiling temperature solvent, dimethyl sulfoxide. The residual solvent in the precursor gel film makes the film moldable upon microprinting with a patterned PDMS mold, leading to various perovskite micropatterns in resolution of a few micrometers over a large area. Our nondestructive micropatterning process does not harm the intrinsic photoelectric properties of a perovskite film, which allows for realizing arrays of parallel-type photodetectors containing micropatterns of a perovskite film with reliable photoconduction performance. The facile transfer of a micropatterned soft-gel precursor film on other substrates including mechanically flexible plastics can further broaden its applications to flexible photoelectric systems.

Methods of producing adsorption media including a metal oxide

DOEpatents

Mann, Nicholas R; Tranter, Troy J

2014-03-04

Methods of producing a metal oxide are disclosed. The method comprises dissolving a metal salt in a reaction solvent to form a metal salt/reaction solvent solution. The metal salt is converted to a metal oxide and a caustic solution is added to the metal oxide/reaction solvent solution to adjust the pH of the metal oxide/reaction solvent solution to less than approximately 7.0. The metal oxide is precipitated and recovered. A method of producing adsorption media including the metal oxide is also disclosed, as is a precursor of an active component including particles of a metal oxide.

Superinsulating Polyisocyanate Based Aerogels: A Targeted Search for the Optimum Solvent System.

PubMed

Zhu, Zhiyuan; Snellings, Geert M B F; Koebel, Matthias M; Malfait, Wim J

2017-05-31

Polyisocyanate based aerogels combine ultralow thermal conductivities with better mechanical properties than silica aerogel, but these properties critically depend on the nature of the gelation solvent, perhaps more so than on any other parameter. Here, we present a systematic study of the relationship between the polyurethane-polyisocyanurate (PUR-PIR) aerogel microstructure, surface area, thermal conductivity, and density and the gelation solvent's Hansen solubility parameters for an industrially relevant PUR-PIR rigid foam formulation. We first investigated aerogels prepared in acetone-dimethyl sulfoxide (DMSO) blends and observed a minimum in thermal conductivity (λ) and maximum in specific surface area for an acetone:DMSO ratio of 85:15 v/v. We then prepared PUR-PIR aerogels in 32 different solvent blends, divided into three series with δ Dispersion , δ Polarity , and δ H-bonding fixed at 15.94, 11.30, and 7.48 MPa 1/2 , respectively, corresponding to the optimum parameters for the acetone:DMSO series. The aerogel properties display distinct dependencies on the various solubility parameters: aerogels with low thermal conductivity can be synthesized in solvents with a high δ H-bonding parameter (above 7.2) and δ Dispersion around 16.3 MPa 1/2 . In contrast, the δ Polarity parameter is of lesser importance. Our study highlights the importance of the gelation solvent, clarifies the influence of the different solvent properties, and provides a methodology for a targeted search across the solvent chemical space based on the Hansen solubility parameters.

Infrared Database for Process Support Materials

NASA Technical Reports Server (NTRS)

Bennett, K. E.; Boothe, R. E.; Burns, H. D.

2003-01-01

Process support materials' compatibility with cleaning processes is critical to ensure final hardware cleanliness and that performance requirements are met. Previous discovery of potential contaminants in process materials shows the need for incoming materials testing and establishment of a process materials database. The Contamination Control Team of the Materials, Processes, and Manufacturing (MP&M) Department at Marshall Space Flight Center (MSFC) has initiated the development of such an infrared (IR) database, called the MSFC Process Materials IR database, of the common process support materials used at MSFC. These process support materials include solvents, wiper cloths, gloves, bagging materials, etc. Testing includes evaluation of the potential of gloves, wiper cloths, and other items to transfer contamination to handled articles in the absence of solvent exposure, and the potential for solvent exposure to induce material degradation. This Technical Memorandum (TM) summarizes the initial testing completed through December 2002. It is anticipated that additional testing will be conducted with updates provided in future TMs.Materials were analyzed using two different IR techniques: (1) Dry transference and (2) liquid extraction testing. The first of these techniques utilized the Nicolet Magna 750 IR spectrometer outfitted with a horizontal attenuated total reflectance (HATR) crystal accessory. The region from 650 to 4,000 wave numbers was analyzed, and 50 scans were performed per IR spectrum. A dry transference test was conducted by applying each sample with hand pressure to the HATR crystal to first obtain a spectrum of the parent material. The material was then removed from the HATR crystal and analyzed to determine the presence of any residues. If volatile, liquid samples were examined both prior to and following evaporation.The second technique was to perform an extraction test with each sample in five different solvents.Once the scans were complete for both the dry transference and the extraction tests, the residue from each scan was interpreted.

Water/alcohol soluble conjugated polymers as highly efficient electron transporting/injection layer in optoelectronic devices.

PubMed

Huang, Fei; Wu, Hongbin; Cao, Yong

2010-07-01

Water/alcohol soluble conjugated polymers (WSCPs) can be processed from water or other polar solvents, which offer good opportunities to avoid interfacial mixing upon fabrication of multilayer polymer optoelectronic devices by solution processing, and can dramatically improve charge injection from high work-function metal cathode resulting in greatly enhancement of the device performance. In this critical review, the authors provide a brief review of recent developments in this field, including the materials design, functional principles, and their unique applications as interface modification layer in solution-processable multilayer optoelectronic devices (135 references).

Essential roles of protein-solvent many-body correlation in solvent-entropy effect on protein folding and denaturation: comparison between hard-sphere solvent and water.

PubMed

Oshima, Hiraku; Kinoshita, Masahiro

2015-04-14

In earlier works, we showed that the entropic effect originating from the translational displacement of water molecules plays the pivotal role in protein folding and denaturation. The two different solvent models, hard-sphere solvent and model water, were employed in theoretical methods wherein the entropic effect was treated as an essential factor. However, there were similarities and differences in the results obtained from the two solvent models. In the present work, to unveil the physical origins of the similarities and differences, we simultaneously consider structural transition, cold denaturation, and pressure denaturation for the same protein by employing the two solvent models and considering three different thermodynamic states for each solvent model. The solvent-entropy change upon protein folding/unfolding is decomposed into the protein-solvent pair (PA) and many-body (MB) correlation components using the integral equation theories. Each component is further decomposed into the excluded-volume (EV) and solvent-accessible surface (SAS) terms by applying the morphometric approach. The four physically insightful constituents, (PA, EV), (PA, SAS), (MB, EV), and (MB, SAS), are thus obtained. Moreover, (MB, SAS) is discussed by dividing it into two factors. This all-inclusive investigation leads to the following results: (1) the protein-water many-body correlation always plays critical roles in a variety of folding/unfolding processes; (2) the hard-sphere solvent model fails when it does not correctly reproduce the protein-water many-body correlation; (3) the hard-sphere solvent model becomes problematic when the dependence of the many-body correlation on the solvent number density and temperature is essential: it is not quite suited to studies on cold and pressure denaturating of a protein; (4) when the temperature and solvent number density are limited to the ambient values, the hard-sphere solvent model is usually successful; and (5) even at the ambient values, however, the many-body correlation plays significant roles in the β-sheet formation and argument of relative stabilities of very similar structures of a protein. These results are argued in detail with respect to the four physically insightful constituents and the two factors mentioned above. The relevance to the absence or presence of hydrogen-bonding properties in the solvent is also discussed in detail.

Essential roles of protein-solvent many-body correlation in solvent-entropy effect on protein folding and denaturation: Comparison between hard-sphere solvent and water

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

Oshima, Hiraku; Kinoshita, Masahiro, E-mail: kinoshit@iae.kyoto-u.ac.jp

In earlier works, we showed that the entropic effect originating from the translational displacement of water molecules plays the pivotal role in protein folding and denaturation. The two different solvent models, hard-sphere solvent and model water, were employed in theoretical methods wherein the entropic effect was treated as an essential factor. However, there were similarities and differences in the results obtained from the two solvent models. In the present work, to unveil the physical origins of the similarities and differences, we simultaneously consider structural transition, cold denaturation, and pressure denaturation for the same protein by employing the two solvent modelsmore » and considering three different thermodynamic states for each solvent model. The solvent-entropy change upon protein folding/unfolding is decomposed into the protein-solvent pair (PA) and many-body (MB) correlation components using the integral equation theories. Each component is further decomposed into the excluded-volume (EV) and solvent-accessible surface (SAS) terms by applying the morphometric approach. The four physically insightful constituents, (PA, EV), (PA, SAS), (MB, EV), and (MB, SAS), are thus obtained. Moreover, (MB, SAS) is discussed by dividing it into two factors. This all-inclusive investigation leads to the following results: (1) the protein-water many-body correlation always plays critical roles in a variety of folding/unfolding processes; (2) the hard-sphere solvent model fails when it does not correctly reproduce the protein-water many-body correlation; (3) the hard-sphere solvent model becomes problematic when the dependence of the many-body correlation on the solvent number density and temperature is essential: it is not quite suited to studies on cold and pressure denaturating of a protein; (4) when the temperature and solvent number density are limited to the ambient values, the hard-sphere solvent model is usually successful; and (5) even at the ambient values, however, the many-body correlation plays significant roles in the β-sheet formation and argument of relative stabilities of very similar structures of a protein. These results are argued in detail with respect to the four physically insightful constituents and the two factors mentioned above. The relevance to the absence or presence of hydrogen-bonding properties in the solvent is also discussed in detail.« less

Blowing bubbles in Lennard-Jonesium along the saturation curve.

PubMed

Ashbaugh, Henry S

2009-05-28

Extensive molecular simulations of the Lennard-Jones fluid have been performed to determine its liquid-vapor coexistence properties and solvent contact densities with cavities up to ten times the diameter of the solvent from the triple point to the critical point. These simulations are analyzed using a revised scaled-particle theory [H. S. Ashbaugh and L. R. Pratt, Rev. Mod. Phys. 78, 159 (2006)] to evaluate the thermodynamics of cavity solvation and curvature dependent interfacial properties along the saturation curve. While the thermodynamic signatures of cavity solvation are distinct from those in water, exhibiting a chemical potential dominated by a large temperature independent enthalpy, the solvent dewets cavities of increasing size similar with water near coexistence. The interfacial tension for forming a liquid-wall interface is found to be consistently greater than the liquid-vapor surface tension of the Lennard-Jones fluid by up to 10% and potentially reflects the suppression of high amplitude fluctuations at the cavity surface. The first-order curvature correction for the surface tension is negative and appears to diverge to negative infinity at temperatures approaching the critical point. Our results point to the success of the revised scaled-particle theory at bridging molecular and macroscopic descriptions of cavity solvation.

Transport of organic solutes through amorphous teflon AF films.

PubMed

Zhao, Hong; Zhang, Jie; Wu, Nianqiang; Zhang, Xu; Crowley, Katie; Weber, Stephen G

2005-11-02

Fluorous media have great potential for selective extraction (e.g., as applied to organic synthesis). Fluorous polymer films would have significant advantages in fluorous separations. Stable films of Teflon AF 2400 were cast from solution. Films appear defect-free (SEM; AFM). Rigid aromatic solutes are transported (from chloroform solution to chloroform receiving phase) in a size-dependent manner (log permeability is proportional to -0.0067 times critical volume). Benzene's permeability is about 2 orders of magnitude higher than in comparable gas-phase experiments. The films show selectivity for fluorinated solutes in comparison to the hydrogen-containing control. Transport rates are dependent on the solvent making up the source and receiving phases. The effect of solvent is, interestingly, not due to changes in partition ratio, but rather it is due to changes in the solute diffusion coefficient in the film. Solvents plasticize the films. A less volatile compound, -COOH-terminated poly(hexafluoropropylene oxide) (4), plasticizes the films (T(g) = -40 degrees C). Permeabilities are decreased in comparison to 4-free films apparently because of decreased diffusivity of solutes. The slope of dependence of log permeability on critical volume is not changed, however.

Separation processes using expulsion from dilute supercritical solutions

DOEpatents

Cochran, Jr., Henry D.

1993-01-01

A process for separating isotopes as well as other mixtures by utilizing the behavior of dilute repulsive or weakly attractive elements of the mixtures as the critical point of the solvent is approached.

Contamination removal using various solvents and methodologies

NASA Technical Reports Server (NTRS)

Jeppsen, J. C.

1989-01-01

Critical and non-critical bonding surfaces must be kept free of contamination that may cause potential unbonds. For example, an aft-dome section of a redesigned solid rocket motor that had been contaminated with hydraulic oil did not appear to be sufficiently cleaned when inspected by the optically stimulated electron emission process (Con Scan) after it had been cleaned using a hand double wipe cleaning method. As a result, current and new cleaning methodologies as well as solvent capability in removing various contaminant materials were reviewed and testing was performed. Bonding studies were also done to verify that the cleaning methods used in removing contaminants provide an acceptable bonding surface. The removal of contaminants from a metal surface and the strength of subsequent bonds were tested using the Martin Marietta and double-wipe cleaning methods. Results are reported.

Method for reprocessing and separating spent nuclear fuels. [Patent application

DOEpatents

Krikorian, O.H.; Grens, J.Z.; Parrish, W.H. Sr.

1982-01-19

Spent nuclear fuels, including actinide fuels, volatile and nonvolatile fission products, are reprocessed and separated in a molten metal solvent housed in a separation vessel made of a carbon-containing material. A first catalyst, which promotes the solubility and permeability of carbon in the metal solvent, is included. By increasing the solubility and permeability of the carbon in the solvent, the rate at which actinide oxides are reduced (carbothermic reduction) is greatly increased. A second catalyst, included to increase the affinity for nitrogen in the metal solvent, is added to increase the rate at which actinide nitrides form after carbothermic reduction is complete.

A sparse autoencoder-based deep neural network for protein solvent accessibility and contact number prediction.

PubMed

Deng, Lei; Fan, Chao; Zeng, Zhiwen

2017-12-28

Direct prediction of the three-dimensional (3D) structures of proteins from one-dimensional (1D) sequences is a challenging problem. Significant structural characteristics such as solvent accessibility and contact number are essential for deriving restrains in modeling protein folding and protein 3D structure. Thus, accurately predicting these features is a critical step for 3D protein structure building. In this study, we present DeepSacon, a computational method that can effectively predict protein solvent accessibility and contact number by using a deep neural network, which is built based on stacked autoencoder and a dropout method. The results demonstrate that our proposed DeepSacon achieves a significant improvement in the prediction quality compared with the state-of-the-art methods. We obtain 0.70 three-state accuracy for solvent accessibility, 0.33 15-state accuracy and 0.74 Pearson Correlation Coefficient (PCC) for the contact number on the 5729 monomeric soluble globular protein dataset. We also evaluate the performance on the CASP11 benchmark dataset, DeepSacon achieves 0.68 three-state accuracy and 0.69 PCC for solvent accessibility and contact number, respectively. We have shown that DeepSacon can reliably predict solvent accessibility and contact number with stacked sparse autoencoder and a dropout approach.

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

PubMed

Rai, Gitanjali; Kumar, Anil

2014-04-17

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

Investigation of Cleanliness Verification Techniques for Rocket Engine Hardware

NASA Technical Reports Server (NTRS)

Fritzemeier, Marilyn L.; Skowronski, Raymund P.

1994-01-01

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

Implementation of Precision Verification Solvents on the External Tank

NASA Technical Reports Server (NTRS)

Campbell, M.

1998-01-01

This paper presents the Implementation of Precision Verification Solvents on the External Tank. The topics include: 1) Background; 2) Solvent Usages; 3) TCE (Trichloroethylene) Reduction; 4) Solvent Replacement Studies; 5) Implementation; 6) Problems Occuring During Implementation; and 7) Future Work. This paper is presented in viewgraph form.

Batch extracting process using magneticparticle held solvents

DOEpatents

Nunez, Luis; Vandergrift, George F.

1995-01-01

A process for selectively removing metal values which may include catalytic values from a mixture containing same, wherein a magnetic particle is contacted with a liquid solvent which selectively dissolves the metal values to absorb the liquid solvent onto the magnetic particle. Thereafter the solvent-containing magnetic particles are contacted with a mixture containing the heavy metal values to transfer metal values into the solvent carried by the magnetic particles, and then magnetically separating the magnetic particles. Ion exchange resins may be used for selective solvents.

Remediation of Contaminated Soils By Supercritical Carbon Dioxide Extraction

NASA Astrophysics Data System (ADS)

Ferri, A.; Zanetti, M. C.; Banchero, M.; Fiore, S.; Manna, L.

The contaminants that can be found in soils are many, inorganic, like heavy metals, as well as organic. Among the organic contaminants, oil and coal refineries are responsi- ble for several cases of soil contamination with PAHs (Polycyclic Aromatic Hydrocar- bons). Polynuclear aromatic hydrocarbons (PAHs) have toxic, carcinogenic and mu- tagenic effects. Limits have been set on the concentration of most contaminants, and growing concern is focusing on soil contamination issues. USA regulations set the maximum acceptable level of contamination by PAHs equal to 40 ppm at residential sites and 270 ppm at industrial sites. Stricter values are usually adopted in European Countries. Supercritical carbon dioxide extraction is a possible alternative technology to remove volatile organic compounds from contaminated soils. Supercritical fluid extraction (SFE) offers many advantages over conventional solvent extraction. Super- critical fluids combine gaseous properties as a high diffusion coefficient, and liquid properties as a high solvent power. The solvent power is strongly pressure-dependent near supercritical conditions: selective extractions are possible without changing the solvent. Solute can be separate from the solvent depressurising the system; therefore, it is possible to recycle the solvent and recover the contaminant. Carbon dioxide is frequently used as supercritical fluid, because it has moderate critical conditions, it is inert and available in pure form. In this work, supercritical fluid extraction technology has been used to remove a polynuclear aromatic hydrocarbon from contaminated soils. The contaminant choice for the experiment has been naphthalene since several data are available in literature. G. A. Montero et al. [1] studied soil remediation with supercrit- ical carbon dioxide extraction technology; these Authors have found that there was a mass-transfer limitation. In the extraction vessel, the mass transfer coefficient in- creases with the superficial velocity of the supercritical carbon dioxide; therefore, the mass transfer resistance can be reduced increasing such velocity. In this work, higher values of superficial velocity were investigated. The experimental apparatus includes a pump, an extraction vessel, an adjustable restrictor and a trap to collect the extracted substance. Liquid carbon dioxide coming from a cylinder with a dip-tube is cooled by a cryostatic bath and then it is compressed by a pneumatic drive pump (the max- imum available pressure is 69 MPa). Subsequently, the pressurised current flows into 1 a heating coil and then into the extraction vessel, which is contained in a stove; the outlet flow is depressurised in an adjustable restrictor and the extracted substance is collected in a trap by dissolution into a solvent. The extracted naphthalene quantity was obtained by weighting the solvent and measuring the naphthalene concentration with a gas chromatograph. The soil sample is a sandy soil geologically representative of the North of Italy that was sampled and physically and chemically characterized: particle-size distribution analysis, diffractometric analysis, Cation Exchange Capac- ity, Total Organic Carbon, iron content and manganese content in order to evaluate the potential sorption degree. The soil was artificially polluted by means of a naphta- lene and methylene chloride solution. The experimental work consists in a number of naphthalene extractions from the spiked soil, that were carried out at different operat- ing conditions, temperature, pressure and flow rate by means of supercritical carbon dioxide evaluating the corresponding recovery efficiencies. The results obtained were analysed and compared in order to determine which parameters influence the system. [1] G. A. Montero, T.D. Giorgio, and K. B. Schnelle, Jr..Removal of Hazardous ,1994, Contaminants form Soils by Supercritical Fluid Extraction. Innovations in Supercriti- cal Fluids. ACS Symposium Series, 608, 280-197. 2

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

Ferrell, Jack R; Ware, Anne E

Two catalytic fast pyrolysis (CFP) oils (bottom/heavy fraction) were analyzed in various solvents that are used in common analytical methods (nuclear magnetic resonance - NMR, gas chromatography - GC, gel permeation chromatography - GPC, thermogravimetric analysis - TGA) for oil characterization and speciation. A more accurate analysis of the CFP oils can be obtained by identification and exploitation of solvent miscibility characteristics. Acetone and tetrahydrofuran can be used to completely solubilize CFP oils for analysis by GC and tetrahydrofuran can be used for traditional organic GPC analysis of the oils. DMSO-d6 can be used to solubilize CFP oils for analysismore » by 13C NMR. The fractionation of oils into solvents that did not completely solubilize the whole oils showed that miscibility can be related to the oil properties. This allows for solvent selection based on physico-chemical properties of the oils. However, based on semi-quantitative comparisons of the GC chromatograms, the organic solvent fractionation schemes did not speciate the oils based on specific analyte type. On the other hand, chlorinated solvents did fractionate the oils based on analyte size to a certain degree. Unfortunately, like raw pyrolysis oil, the matrix of the CFP oils is complicated and is not amenable to simple liquid-liquid extraction (LLE) or solvent fractionation to separate the oils based on the chemical and/or physical properties of individual components. For reliable analyses, for each analytical method used, it is critical that the bio-oil sample is both completely soluble and also not likely to react with the chosen solvent. The adoption of the standardized solvent selection protocols presented here will allow for greater reproducibility of analysis across different users and facilities.« less

Reinventing Design Principles for Developing Low-Viscosity Carbon Dioxide-Binding Organic Liquids for Flue Gas Clean Up.

PubMed

Malhotra, Deepika; Koech, Phillip K; Heldebrant, David J; Cantu, David C; Zheng, Feng; Glezakou, Vassiliki-Alexandra; Rousseau, Roger

2017-02-08

Anthropogenic CO 2 emissions from point sources (e.g., coal fired-power plants) account for the majority of the greenhouse gases in the atmosphere. Water-lean solvent systems such as CO 2 -binding organic liquids (CO 2 BOLs) are being developed to reduce the energy requirement for CO 2 capture. Many water-lean solvents such as CO 2 BOLs are currently limited by the high viscosities of concentrated electrolyte solvents, thus many of these solvents have yet to move toward commercialization. Conventional standard trial-and-error approaches for viscosity reduction, while effective, are time consuming and economically expensive. We rethink the metrics and design principles of low-viscosity CO 2 -capture solvents using a combined synthesis and computational modeling approach. We critically study the effects of viscosity reducing factors such as orientation of hydrogen bonding, introduction of higher degrees of freedom, and cation or anion charge solvation, and assess whether or how each factor affects viscosity of CO 2 BOL CO 2 capture solvents. Ultimately, we found that hydrogen bond orientation and strength is the predominant factor influencing the viscosity in CO 2 BOL solvents. With this knowledge, a new CO 2 BOL variant, 1-MEIPADM-2-BOL, was synthesized and tested, resulting in a solvent that is approximately 60 % less viscous at 25 mol % CO 2 loading than our base compound 1-IPADM-2-BOL. The insights gained from the current study redefine the fundamental concepts and understanding of what influences viscosity in concentrated organic CO 2 -capture solvents. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Liquid Salt as Green Solvent: A Novel Eco-Friendly Technique to Enhance Solubility and Stability of Poorly Soluble Drugs

NASA Astrophysics Data System (ADS)

Patel, Anant A.

As a result of tremendous efforts in past few decades, various techniques have been developed in order to resolve solubility issues associated with class II and IV drugs, However, majority of these techniques offer benefits associated with certain drawbacks; majorly including low drug loading, physical instability on storage and excessive use of environmentally challenging organic solvents. Hence, current effort was to develop an eco-friendly technique using liquid salt as green solvent, which can offer improvement in dissolution while maintaining long term stability. The liquid salt formulations (LSF) of poorly soluble model drugs ibuprofen, gemfibrozil and indomethacin were developed using 1-Ethyl-3-methylimidazolium ethyl sulfate (EMIM ES) as a non-toxic and environmentally friendly alternate to organic solvents. Liquid medications containing clear solutions of drug, EMIM ES and polysorbate 20, were adsorbed onto porous carrier Neusilin US2 to form free flowing powder. The LSF demonstrated greater rate and extent of dissolution compared to crystalline drugs. The dissolution data revealed that more than 80% drug release from LSF within 20 mins compared to less than 18% release from pure drugs. As high as 70% w/w liquid loading was achieved while maintaining good flowability and compressibility. In addition, the LSF samples exposed to high temperature and high humidity i.e. 40°C/80% RH for 8 weeks, demonstrated excellent physical stability without any signs of precipitation or crystallization. As most desirable form of administration is tablet, the developed liquid salt formulations were transformed into tablets using design of experiment approach by Design Expert Software. The tablet formulation composition and critical parameter were optimized using Box-Behnken Design. This innovative liquid salt formulation technique offered improvement in dissolution rate and extent as well as contributed to excellent physical stability on storage. Moreover, this formulation approach served as eco-friendly compelling alternate to conventional techniques involving organic solvents.

Separation processes using expulsion from dilute supercritical solutions

DOEpatents

Cochran, H.D. Jr.

1993-04-20

A process is described for separating isotopes as well as other mixtures by utilizing the behavior of dilute repulsive or weakly attractive elements of the mixtures as the critical point of the solvent is approached.

Poly(ethylene glycol)-based ionic liquids: properties and uses as alternative solvents in organic synthesis and catalysis.

PubMed

Cecchini, Martina Maya; Charnay, Clarence; De Angelis, Francesco; Lamaty, Frédéric; Martinez, Jean; Colacino, Evelina

2014-01-01

PEG-based ionic liquids are a new appealing group of solvents making the link between two distinct but very similar fluids: ionic liquids and poly(ethylene glycol)s. They find applications across a range of innumerable disciplines in science, technology, and engineering. In the last years, the possibility to use these as alternative solvents for organic synthesis and catalysis has been increasingly explored. This Review highlights strategies for their synthesis, their physical properties (critical point, glass transition temperature, density, rheological properties), and their application in reactions catalyzed by metals (such as Pd, Cu, W, or Rh) or as organic solvent (for example for multicomponent reactions, organocatalysis, CO2 transformation) with special emphasis on their toxicity, environmental impact, and biodegradability. These aspects, very often neglected, need to be considered in addition to the green criteria usually considered to establish ecofriendly processes. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Selective free radical reactions using supercritical carbon dioxide.

PubMed

Cormier, Philip J; Clarke, Ryan M; McFadden, Ryan M L; Ghandi, Khashayar

2014-02-12

We report herein a means to modify the reactivity of alkenes, and particularly to modify their selectivity toward reactions with nonpolar reactants (e.g., nonpolar free radicals) in supercritical carbon dioxide near the critical point. Rate constants for free radical addition of the light hydrogen isotope muonium to ethylene, vinylidene fluoride, and vinylidene chloride in supercritical carbon dioxide are compared over a range of pressures and temperatures. Near carbon dioxide's critical point, the addition to ethylene exhibits critical speeding up, while the halogenated analogues display critical slowing. This suggests that supercritical carbon dioxide as a solvent may be used to tune alkene chemistry in near-critical conditions.

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

PubMed

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

2017-06-02

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

Development of deep eutectic solvents applied in extraction and separation.

PubMed

Li, Xiaoxia; Row, Kyung Ho

2016-09-01

Deep eutectic solvents, as an alternative to ionic liquids, have greener credentials than ionic liquids, and have attracted considerable attention in related chemical research. Deep eutectic solvents have attracted increasing attention in chemistry for the extraction and separation of various target compounds from natural products. This review highlights the preparation of deep eutectic solvents, unique properties of deep eutectic solvents, and synthesis of deep-eutectic-solvent-based materials. On the other hand, application in the extraction and separation of deep eutectic solvents is also included in this report. In this paper, the available data and references in this field are reviewed to summarize the applications and developments of deep eutectic solvents. Based on the development of deep eutectic solvents, an exploitation of new deep eutectic solvents and deep eutectic solvents-based materials is expected to diversify into extraction and separation. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Systems and methods for producing metal clusters; functionalized surfaces; and droplets including solvated metal ions

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

Cooks, Robert Graham; Li, Anyin; Luo, Qingjie

The invention generally relates to systems and methods for producing metal clusters; functionalized surfaces; and droplets including solvated metal ions. In certain aspects, the invention provides methods that involve providing a metal and a solvent. The methods additionally involve applying voltage to the solvated metal to thereby produce solvent droplets including ions of the metal containing compound, and directing the solvent droplets including the metal ions to a target. In certain embodiments, once at the target, the metal ions can react directly or catalyze reactions.

Systems and methods for producing metal clusters; functionalized surfaces; and droplets including solvated metal ions

DOEpatents

Cooks, Robert Graham; Li, Anyin; Luo, Qingjie

2017-01-24

The invention generally relates to systems and methods for producing metal clusters; functionalized surfaces; and droplets including solvated metal ions. In certain aspects, the invention provides methods that involve providing a metal and a solvent. The methods additionally involve applying voltage to the solvated metal to thereby produce solvent droplets including ions of the metal containing compound, and directing the solvent droplets including the metal ions to a target. In certain embodiments, once at the target, the metal ions can react directly or catalyze reactions.

Understanding the influence of solvent field and fluctuations on the stability of photo-induced charge-separated state in molecular triad

NASA Astrophysics Data System (ADS)

Balamurugan, D.; Aquino, Adelia; Lischka, Hans; Dios, Francis; Flores, Lionel; Cheung, Margaret

2013-03-01

Molecular triad composed of fullerene, porphyrin, and carotene is an artificial analogue of natural photosynthetic system and is considered for applications in solar energy conversion because of its ability to produce long-lived photo-induced charge separated state. The goal of the present multiscale simulation is to understand how the stability of photo-induced charge-separated state in molecular triad is influenced by a polar organic solvent, namely tetrahydrofuran (THF). The multiscale approach is based on combined quantum, classical molecular dynamics, and statistical physics calculations. The quantum chemical calculations were performed on the triad using the second order algebraic diagrammatic perturbation and time-dependent density functional theory. Molecular dynamics simulations were performed on triad in a box of THF solvent with the replica exchange method. The two methods on different length and time scales are bridged through an important sampling technique. We have analyzed the free energy landscape, structural fluctuations, and the long- range electrostatic interactions between triad and solvent molecules. The results suggest that the polarity and re-organization of the solvent is critical in stabilization of charge-separated state in triad. Supported by DOE (DE-FG02-10ER16175)

Implementation of quality by design principles in the development of microsponges as drug delivery carriers: Identification and optimization of critical factors using multivariate statistical analyses and design of experiments studies.

PubMed

Simonoska Crcarevska, Maja; Dimitrovska, Aneta; Sibinovska, Nadica; Mladenovska, Kristina; Slavevska Raicki, Renata; Glavas Dodov, Marija

2015-07-15

Microsponges drug delivery system (MDDC) was prepared by double emulsion-solvent-diffusion technique using rotor-stator homogenization. Quality by design (QbD) concept was implemented for the development of MDDC with potential to be incorporated into semisolid dosage form (gel). Quality target product profile (QTPP) and critical quality attributes (CQA) were defined and identified, accordingly. Critical material attributes (CMA) and Critical process parameters (CPP) were identified using quality risk management (QRM) tool, failure mode, effects and criticality analysis (FMECA). CMA and CPP were identified based on results obtained from principal component analysis (PCA-X&Y) and partial least squares (PLS) statistical analysis along with literature data, product and process knowledge and understanding. FMECA identified amount of ethylcellulose, chitosan, acetone, dichloromethane, span 80, tween 80 and water ratio in primary/multiple emulsions as CMA and rotation speed and stirrer type used for organic solvent removal as CPP. The relationship between identified CPP and particle size as CQA was described in the design space using design of experiments - one-factor response surface method. Obtained results from statistically designed experiments enabled establishment of mathematical models and equations that were used for detailed characterization of influence of identified CPP upon MDDC particle size and particle size distribution and their subsequent optimization. Copyright © 2015 Elsevier B.V. All rights reserved.

The role of ultra-fast solvent evaporation on the directed self-assembly of block polymer thin films

NASA Astrophysics Data System (ADS)

Drapes, Chloe; Nelson, G.; Grant, M.; Wong, J.; Baruth, A.

The directed self-assembly of nano-structures in block polymer thin films viasolvent vapor annealing is complicated by several factors, including evaporation rate. Solvent vapor annealing exposes a disordered film to solvent(s) in the vapor phase, increasing mobility and tuning surface energy, with the intention of producing an ordered structure. Recent theoretical predictions reveal the solvent evaporation affects the resultant nano-structuring. In a competition between phase separation and kinetic trapping during drying, faster solvent removal can enhance the propagation of a given morphology into the bulk of the thin film down to the substrate. Recent construction of a purpose-built, computer controlled solvent vapor annealing chamber provides control over forced solvent evaporation down to 15 ms. This is accomplished using pneumatically actuated nitrogen flow into and out of the chamber. Furthermore, in situ spectral reflectance, with 10 ms temporal resolution, monitors the swelling and evaporation. Presently, cylinder-forming polystyrene-block-polylactide thin films were swollen with 40% (by volume) tetrahydrofuran, followed by immediate evaporation under a variety of designed conditions. This includes various evaporation times, ranging from 15 ms to several seconds, and four unique rate trajectories, including linear, exponential, and combinations. Atomic force microscopy reveals specific surface, free and substrate, morphologies of the resultant films, dependent on specific evaporation conditions. Funded by the Clare Boothe Luce Foundation and Nebraska EPSCoR.

A biomolecular electrostatics solver using Python, GPUs and boundary elements that can handle solvent-filled cavities and Stern layers.

PubMed

Cooper, Christopher D; Bardhan, Jaydeep P; Barba, L A

2014-03-01

The continuum theory applied to biomolecular electrostatics leads to an implicit-solvent model governed by the Poisson-Boltzmann equation. Solvers relying on a boundary integral representation typically do not consider features like solvent-filled cavities or ion-exclusion (Stern) layers, due to the added difficulty of treating multiple boundary surfaces. This has hindered meaningful comparisons with volume-based methods, and the effects on accuracy of including these features has remained unknown. This work presents a solver called PyGBe that uses a boundary-element formulation and can handle multiple interacting surfaces. It was used to study the effects of solvent-filled cavities and Stern layers on the accuracy of calculating solvation energy and binding energy of proteins, using the well-known apbs finite-difference code for comparison. The results suggest that if required accuracy for an application allows errors larger than about 2% in solvation energy, then the simpler, single-surface model can be used. When calculating binding energies, the need for a multi-surface model is problem-dependent, becoming more critical when ligand and receptor are of comparable size. Comparing with the apbs solver, the boundary-element solver is faster when the accuracy requirements are higher. The cross-over point for the PyGBe code is in the order of 1-2% error, when running on one gpu card (nvidia Tesla C2075), compared with apbs running on six Intel Xeon cpu cores. PyGBe achieves algorithmic acceleration of the boundary element method using a treecode, and hardware acceleration using gpus via PyCuda from a user-visible code that is all Python. The code is open-source under MIT license.

Simultaneous destraction and desulfurization of Illinois coals with supercritical ethanol

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

Wu, B.C.

1983-01-01

Various Illinois coals (with Illinois number6 being the main one) are liquefied with various supercritical solvents (ethanol being the main solvent) at 543-598 K, system pressures of 6.99-24.23 MPa, flow rates of 3.0-7.5 ml/min, reaction time of 0-180 minutes, and coal particle sizes of 0.36-0.85 mm to 1.00-2.36 mm to systematically investigate the effects of flow rates, reaction time, coal particle size, temperature, pressure, coal characteristics (by using different Illinois coals), supercritical medium (by using different solvents), and the addition of potassium hydroxide. The % weight loss of coal and the % sulfur removal during destraction and desulfurization of coalmore » are functions of the flow rate, the reaction time, the coal particle size, temperature, pressure and the supercritical solvent. Temperature, pressure and the supercritical medium are the most important parameters in controlling the % weight loss of coal and the % sulfur removal. The % weight loss of coal can be related to a power law and fits quite nicely into a second order kinetic model. The % sulfur removal also follows a second order kinetic model. A secondary reaction is observed during the destraction process, which implies that destraction, and possibly desulfurization, of coal is a multistep reaction including a physical extraction step where the major portion of the coal and sulfur was removed and then followed by a chemical reaction. Supercritical ethanol definitely enhances the removal of sulfur compounds from coal. The enhanced selectivity by supercritical ethanol is greatest at a pressure just above the critical pressure of ethanol. Finally, addition of a base such as potassium hydroxide enhances both % weight loss of coal and the % sulfur removal.« less

A biomolecular electrostatics solver using Python, GPUs and boundary elements that can handle solvent-filled cavities and Stern layers

NASA Astrophysics Data System (ADS)

Cooper, Christopher D.; Bardhan, Jaydeep P.; Barba, L. A.

2014-03-01

The continuum theory applied to biomolecular electrostatics leads to an implicit-solvent model governed by the Poisson-Boltzmann equation. Solvers relying on a boundary integral representation typically do not consider features like solvent-filled cavities or ion-exclusion (Stern) layers, due to the added difficulty of treating multiple boundary surfaces. This has hindered meaningful comparisons with volume-based methods, and the effects on accuracy of including these features has remained unknown. This work presents a solver called PyGBe that uses a boundary-element formulation and can handle multiple interacting surfaces. It was used to study the effects of solvent-filled cavities and Stern layers on the accuracy of calculating solvation energy and binding energy of proteins, using the well-known APBS finite-difference code for comparison. The results suggest that if required accuracy for an application allows errors larger than about 2% in solvation energy, then the simpler, single-surface model can be used. When calculating binding energies, the need for a multi-surface model is problem-dependent, becoming more critical when ligand and receptor are of comparable size. Comparing with the APBS solver, the boundary-element solver is faster when the accuracy requirements are higher. The cross-over point for the PyGBe code is on the order of 1-2% error, when running on one GPU card (NVIDIA Tesla C2075), compared with APBS running on six Intel Xeon CPU cores. PyGBe achieves algorithmic acceleration of the boundary element method using a treecode, and hardware acceleration using GPUs via PyCuda from a user-visible code that is all Python. The code is open-source under MIT license.

Photophysical parameters and fluorescence quenching of 7-diethylaminocoumarin (DEAC) laser dye

NASA Astrophysics Data System (ADS)

El-Mossalamy, E. H.; Obaid, A. Y.; El-Daly, S. A.

2011-10-01

The optical properties including electronic absorption spectrum, emission spectrum, fluorescence quantum yield, and dipole moment of electronic transition of 7-diethylaminocoumarin (DEAC) laser dye have been measured in different solvents. Both electronic absorption and fluorescence spectra are red shifted as the polarity of the medium increases, indicating that the dipole moment of molecule increases on excitation. The fluorescence quantum yield of DEAC decreases as the polarity of solvent increases, a result of the role of solvent polarity in stabilization of the twisting of the intramolecular charge transfer (TICT) in excited state, which is a non-emissive state, as well as hydrogen bonding with the hetero-atom of dye. The emission spectrum of DEAC has also been measured in cationic (CTAC) and anionic (SDS) micelles, the intensity increases as the concentration of surfactant increases, and an abrupt change in emission intensity is observed at critical micelle concentration (CMC) of surfactant. 2×10 -3 mol dm -3 of DEAC gives laser emission in the blue region on pumping with nitrogen laser ( λex=337.1 nm). The laser parameters such as tuning range, gain coefficient ( α), emission cross section ( σe), and half-life energy have been calculated in different solvents, namely acetone, dioxane , ethanol, and dimethyforamide (DMF). The photoreactivity of DEAC has been studied in CCl 4 at a wavelength of 366 nm. The values of photochemical yield ( ϕc) and rate constant ( k) are determined. The interaction of organic acceptors such as picric acid (PA), tetracyanoethylene (TCNE), and 7,7,8,8-tetracynoquinonedimethane (TCNQ) with DEAC is also studied using fluorescence measurements in acetonitrile (CH 3CN); from fluorescence quenching study we assume the possible electron transfer from excited donor DEAC to organic acceptor forming non-emissive exciplex.

Batch extracting process using magnetic particle held solvents

DOEpatents

Nunez, L.; Vandergrift, G.F.

1995-11-21

A process is described for selectively removing metal values which may include catalytic values from a mixture containing same, wherein a magnetic particle is contacted with a liquid solvent which selectively dissolves the metal values to absorb the liquid solvent onto the magnetic particle. Thereafter the solvent-containing magnetic particles are contacted with a mixture containing the heavy metal values to transfer metal values into the solvent carried by the magnetic particles, and then magnetically separating the magnetic particles. Ion exchange resins may be used for selective solvents. 5 figs.

Benchmark of ReaxFF force field for subcritical and supercritical water.

PubMed

Manzano, Hegoi; Zhang, Weiwei; Raju, Muralikrishna; Dolado, Jorge S; López-Arbeloa, Iñigo; van Duin, Adri C T

2018-06-21

Water in the subcritical and supercritical states has remarkable properties that make it an excellent solvent for oxidation of hazardous chemicals, waste separation, and green synthesis. Molecular simulations are a valuable complement to experiments in order to understand and improve the relevant sub- and super-critical reaction mechanisms. Since water molecules under these conditions can act not only as a solvent but also as a reactant, dissociative force fields are especially interesting to investigate these processes. In this work, we evaluate the capacity of the ReaxFF force field to reproduce the microstructure, hydrogen bonding, dielectric constant, diffusion, and proton transfer of sub- and super-critical water. Our results indicate that ReaxFF is able to simulate water properties in these states in very good quantitative agreement with the existing experimental data, with the exception of the static dielectric constant that is reproduced only qualitatively.

The interfacial, emulsification and encapsulation properties of hydrophobically modified inulin.

PubMed

Kokubun, S; Ratcliffe, I; Williams, P A

2018-08-15

Octenyl- and dodecenyl succinic anhydride derivatives (OSA- and DDSA-) of inulin have been synthesised and their solution and interfacial properties have been determined and compared to a commercially available alkylated inulin, Inutec SP1. All samples formed micellar aggregates in solution above a critical concentration (critical aggregation concentration) and were able to 'dissolve' a hydrophobic dye. They were also able to form stable oil-in-water (O/W) emulsions as assessed by measurements of their droplet size as a function of time. DDSA-inulin with a high degree of substitution was found to be effective at encapsulating beta carotene using the solvent evaporation method which yielded a solid which dissolved readily in simulated gastric fluid. The results confirm the potential application of these materials in a number of areas including, drug delivery, pharmaceuticals, neutraceuticals, cosmetics and personal care. Copyright © 2018 Elsevier Ltd. All rights reserved.

System for removing contaminants from plastic resin

DOEpatents

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

2010-11-23

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

The Ideal Solvent for Paper Chromatography of Food Dyes.

ERIC Educational Resources Information Center

Markow, Peter G.

1988-01-01

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

Nuclear and chemical safety analysis: Purex Plant 1970 thorium campaign

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

Boldt, A.L.; Oberg, G.C.

The purpose of this document is to discuss the flowsheet and the related processing equipment with respect to nuclear and chemical safety. The analyses presented are based on equipment utilization and revised piping as outlined in the design criteria. Processing of thorium and uranium-233 in the Purex Plant can be accomplished within currently accepted levels of risk with respect to chemical and nuclear safety if minor instrumentation changes are made. Uranium-233 processing is limited to a rate of about 670 grams per hour by equipment capacities and criticality safety considerations. The major criticality prevention problems result from the potential accumulationmore » of uranium-233 in a solvent phase in E-H4 (ICU concentrator), TK-J1 (IUC receiver), and TK-J21 (2AF pump tank). The same potential problems exist in TK-J5 (3AF pump tank) and TK-N1 (3BU receiver), but the probabilities of reaching a critical condition are not as great. In order to prevent the excessive accumulation of uranium-233 in any of these vessels by an extraction mechanism, it is necessary to maintain the uranium-233 and salting agent concentrations below the point at which a critical concentration of uranium-233 could be reached in a solvent phase.« less

Process for heating coal-oil slurries

DOEpatents

Braunlin, W.A.; Gorski, A.; Jaehnig, L.J.; Moskal, C.J.; Naylor, J.D.; Parimi, K.; Ward, J.V.

1984-01-03

Controlling gas to slurry volume ratio to achieve a gas holdup of about 0.4 when heating a flowing coal-oil slurry and a hydrogen containing gas stream allows operation with virtually any coal to solvent ratio and permits operation with efficient heat transfer and satisfactory pressure drops. The critical minimum gas flow rate for any given coal-oil slurry will depend on numerous factors such as coal concentration, coal particle size distribution, composition of the solvent (including recycle slurries), and type of coal. Further system efficiency can be achieved by operating with multiple heating zones to provide a high heat flux when the apparent viscosity of the gas saturated slurry is highest. Operation with gas flow rates below the critical minimum results in system instability indicated by temperature excursions in the fluid and at the tube wall, by a rapid increase and then decrease in overall pressure drop with decreasing gas flow rate, and by increased temperature differences between the temperature of the bulk fluid and the tube wall. At the temperatures and pressures used in coal liquefaction preheaters the coal-oil slurry and hydrogen containing gas stream behaves essentially as a Newtonian fluid at shear rates in excess of 150 sec[sup [minus]1]. The gas to slurry volume ratio should also be controlled to assure that the flow regime does not shift from homogeneous flow to non-homogeneous flow. Stable operations have been observed with a maximum gas holdup as high as 0.72. 29 figs.

Process for heating coal-oil slurries

DOEpatents

Braunlin, Walter A.; Gorski, Alan; Jaehnig, Leo J.; Moskal, Clifford J.; Naylor, Joseph D.; Parimi, Krishnia; Ward, John V.

1984-01-03

Controlling gas to slurry volume ratio to achieve a gas holdup of about 0.4 when heating a flowing coal-oil slurry and a hydrogen containing gas stream allows operation with virtually any coal to solvent ratio and permits operation with efficient heat transfer and satisfactory pressure drops. The critical minimum gas flow rate for any given coal-oil slurry will depend on numerous factors such as coal concentration, coal particle size distribution, composition of the solvent (including recycle slurries), and type of coal. Further system efficiency can be achieved by operating with multiple heating zones to provide a high heat flux when the apparent viscosity of the gas saturated slurry is highest. Operation with gas flow rates below the critical minimum results in system instability indicated by temperature excursions in the fluid and at the tube wall, by a rapid increase and then decrease in overall pressure drop with decreasing gas flow rate, and by increased temperature differences between the temperature of the bulk fluid and the tube wall. At the temperatures and pressures used in coal liquefaction preheaters the coal-oil slurry and hydrogen containing gas stream behaves essentially as a Newtonian fluid at shear rates in excess of 150 sec.sup. -1. The gas to slurry volume ratio should also be controlled to assure that the flow regime does not shift from homogeneous flow to non-homogeneous flow. Stable operations have been observed with a maximum gas holdup as high as 0.72.

Understanding the colloidal dispersion stability of 1D and 2D materials: Perspectives from molecular simulations and theoretical modeling.

PubMed

Lin, Shangchao; Shih, Chih-Jen; Sresht, Vishnu; Govind Rajan, Ananth; Strano, Michael S; Blankschtein, Daniel

2017-06-01

The colloidal dispersion stability of 1D and 2D materials in the liquid phase is critical for scalable nano-manufacturing, chemical modification, composites production, and deployment as conductive inks or nanofluids. Here, we review recent computational and theoretical studies carried out by our group to model the dispersion stability of 1D and 2D materials, including single-walled carbon nanotubes, graphene, and graphene oxide in aqueous surfactant solutions or organic solvents. All-atomistic (AA) molecular dynamics (MD) simulations can probe the molecular level details of the adsorption morphology of surfactants and solvents around these materials, as well as quantify the interaction energy between the nanomaterials mediated by surfactants or solvents. Utilizing concepts from reaction kinetics and diffusion, one can directly predict the rate constants for the aggregation kinetics and dispersion life times using MD outputs. Furthermore, the use of coarse-grained (CG) MD simulations allows quantitative prediction of surfactant adsorption isotherms. Combined with the Poisson-Boltzmann equation, the Langmuir isotherm, and the DLVO theory, one can directly use CGMD outputs to: (i) predict electrostatic potentials around the nanomaterial, (ii) correlate surfactant surface coverages with surfactant concentrations in the bulk dispersion medium, and (iii) determine energy barriers against coagulation. Finally, we discuss challenges associated with studying emerging 2D materials, such as, hexagonal boron nitride (h-BN), phosphorene, and transition metal dichalcogenides (TMDCs), including molybdenum disulfide (MoS 2 ). An outlook is provided to address these challenges with plans to develop force-field parameters for MD simulations to enable predictive modeling of emerging 2D materials in the liquid phase. Copyright © 2016 Elsevier B.V. All rights reserved.

Environmental Hazards Education for Childbirth Educators

PubMed Central

Ondeck, Michele; Focareta, Judith

2009-01-01

The purpose of this article is to educate childbirth educators about environmental hazards and provide resources. Hazardous chemicals have been found in cord blood, placenta, meconium, and breastmilk samples. These chemicals include commonly known hazards such as lead, mercury, and environmental tobacco smoke, as well as some pesticides, solvents, products containing chlorine, and other chemicals referred to as “persistent organic pollutants.” The fetus is particularly vulnerable to environmental chemicals that can disrupt the developmental process at critical times during gestation. Childbirth educators are encouraged to inform themselves in order to inform childbearing families to take preventive action and explore alternative behaviors to reduce exposure to environmental hazards. PMID:20808430

Amorphous or Crystalline? A Comparison of Particle Engineering Methods and Selection.

PubMed

Thakkar, Sachin G; Fathe, Kristin; Smyth, Hugh D C

2015-01-01

This review is intended to provide a critical account of the current goals and technologies of particle engineering regarding the production of crystalline and amorphous particles. The technologies discussed here cover traditional crystallization technologies, supercritical fluid technologies, spray drying, controlled solvent crystallization, and sonocrystallization. Also recent advancements in particle engineering including spray freezing into liquid, thin-film freeze-drying, PRINT technology are presented. The paper also examines the merits and limitations of these technologies with respect to their methods of characterization. Additionally a section discussing the utility of creating amorphous and crystalline formulation approaches in regards to bioavailability and utility in formulation is presented.

Reaction Mechanism of Organocatalytic Michael Addition of Nitromethane to Cinnamaldehyde: A Case Study on Catalyst Regeneration and Solvent Effects.

PubMed

Świderek, Katarzyna; Nödling, Alexander R; Tsai, Yu-Hsuan; Luk, Louis Y P; Moliner, Vicent

2018-01-11

The Michael addition of nitromethane to cinnamaldehyde has been computationally studied in the absence of a catalyst and the presence of a biotinylated secondary amine by a combined computational and experimental approach. The calculations were performed at the density functional theory (DFT) level with the M06-2X hybrid functional, and a polarizable continuum model has been employed to mimic the effect of two different solvents: dichloromethane (DCM) and water. Contrary to common assumption, the product-derived iminium intermediate was absent in both of the solvents tested. Instead, hydrating the C1-C2 double bond in the enamine intermediate directly yields the tetrahedral intermediate, which is key for forming the product and regenerating the catalyst. Enamine hydration is concerted and found to be rate-limiting in DCM but segregated into two non-rate-limiting steps when the solvent is replaced with water. However, further analysis revealed that the use of water as solvent also raises the energy barriers for other chemical steps, particularly the critical step of C-C bond formation between the iminium intermediate and nucleophile; this consequently lowers both the reaction yield and enantioselectivity of this LUMO-lowering reaction, as experimentally detected. These findings provide a logical explanation to why water often enhances organocatalysis when used as an additive but hampers the reaction progress when employed as a solvent.

Reaction Mechanism of Organocatalytic Michael Addition of Nitromethane to Cinnamaldehyde: A Case Study on Catalyst Regeneration and Solvent Effects

PubMed Central

2017-01-01

The Michael addition of nitromethane to cinnamaldehyde has been computationally studied in the absence of a catalyst and the presence of a biotinylated secondary amine by a combined computational and experimental approach. The calculations were performed at the density functional theory (DFT) level with the M06-2X hybrid functional, and a polarizable continuum model has been employed to mimic the effect of two different solvents: dichloromethane (DCM) and water. Contrary to common assumption, the product-derived iminium intermediate was absent in both of the solvents tested. Instead, hydrating the C1–C2 double bond in the enamine intermediate directly yields the tetrahedral intermediate, which is key for forming the product and regenerating the catalyst. Enamine hydration is concerted and found to be rate-limiting in DCM but segregated into two non-rate-limiting steps when the solvent is replaced with water. However, further analysis revealed that the use of water as solvent also raises the energy barriers for other chemical steps, particularly the critical step of C–C bond formation between the iminium intermediate and nucleophile; this consequently lowers both the reaction yield and enantioselectivity of this LUMO-lowering reaction, as experimentally detected. These findings provide a logical explanation to why water often enhances organocatalysis when used as an additive but hampers the reaction progress when employed as a solvent. PMID:29256614

Methods for recovering a polar solvent from a fluid stream contaminated with at least one polar impurity

DOEpatents

Ginosar, Daniel M.; Wendt, Daniel S.

2012-11-13

A method of removing a polar solvent from a fluid volume contaminated with at least one polar impurity, such as a free fatty acid, is provided. The method comprises providing a fluid volume that includes at least one polar impurity dissolved in at least one solvent. The fluid volume is contacted with an expanding gas to remove the at least one solvent. The expanding gas may be dissolved into the at least one solvent in the fluid volume to form a gas-expanded solvent. The immiscibility of the polar impurities in the gas-expanded solvent enables separation of the polar impurities from the gas-expanded solvent. After separation of the polar impurities, at least one of the temperature and pressure may be reduced to separate the solvent from the expanding gas such that the clean solvent may be reused.

40 CFR 63.821 - Designation of affected sources.

Code of Federal Regulations, 2013 CFR

2013-07-01

... presses and all related equipment, including proof presses, cylinder and parts cleaners, ink and solvent... mass of inks, coatings, varnishes, adhesives, primers, solvents, thinners, reducers, and other... inks, coatings, varnishes, adhesives, primers, solvents, thinners, reducers, and other materials...

40 CFR 63.821 - Designation of affected sources.

Code of Federal Regulations, 2012 CFR

2012-07-01

... presses and all related equipment, including proof presses, cylinder and parts cleaners, ink and solvent... mass of inks, coatings, varnishes, adhesives, primers, solvents, thinners, reducers, and other... inks, coatings, varnishes, adhesives, primers, solvents, thinners, reducers, and other materials...

40 CFR 63.821 - Designation of affected sources.

Code of Federal Regulations, 2014 CFR

2014-07-01

... presses and all related equipment, including proof presses, cylinder and parts cleaners, ink and solvent... mass of inks, coatings, varnishes, adhesives, primers, solvents, thinners, reducers, and other... inks, coatings, varnishes, adhesives, primers, solvents, thinners, reducers, and other materials...

Femtosecond dynamics in hydrogen-bonded solvents

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

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

1993-09-01

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

Coal liquefaction process

DOEpatents

Skinner, Ronald W.; Tao, John C.; Znaimer, Samuel

1985-01-01

This invention relates to an improved process for the production of liquid carbonaceous fuels and solvents from carbonaceous solid fuels, especially coal. The claimed improved process includes the hydrocracking of the light SRC mixed with a suitable hydrocracker solvent. The recycle of the resulting hydrocracked product, after separation and distillation, is used to produce a solvent for the hydrocracking of the light solvent refined coal.

40 CFR 63.2854 - How do I determine the weighted average volume fraction of HAP in the actual solvent loss?

Code of Federal Regulations, 2011 CFR

2011-07-01

... Extraction for Vegetable Oil Production Compliance Requirements § 63.2854 How do I determine the weighted... received for use in your vegetable oil production process. By the end of each calendar month following an... the solvent in each delivery of solvent, including solvent recovered from off-site oil. To determine...

40 CFR 63.2854 - How do I determine the weighted average volume fraction of HAP in the actual solvent loss?

Code of Federal Regulations, 2010 CFR

2010-07-01

... Extraction for Vegetable Oil Production Compliance Requirements § 63.2854 How do I determine the weighted... received for use in your vegetable oil production process. By the end of each calendar month following an... the solvent in each delivery of solvent, including solvent recovered from off-site oil. To determine...

Free energy landscape for glucose condensation reactions.

PubMed

Liu, Dajiang; Nimlos, Mark R; Johnson, David K; Himmel, Michael E; Qian, Xianghong

2010-12-16

Ab initio molecular dynamics and metadynamics simulations were used to determine the free energy surfaces (FES) for the acid catalyzed β-D-glucose condensation reaction. Protonation of C1-OH on the β-D-glucose, breakage of the C1-O1 bond, and the formation of C1 carbocation is the rate-limiting step. The effects of solvent on the reaction were investigated by determining the FES both in the absence and presence of solvent water. It was found that water played a critical role in these reactions. The reaction barrier for the proton-catalyzed glucose condensation reaction is solvent induced because of proton's high affinity for water. During these simulations, β-D-glucose conversion to α-d-glucose process via the C1 carbocation was also observed. The associated free energy change and activation barrier for this reaction were determined.

Use of normal propyl bromide solvents for extraction and recovery of asphalt cements

DOT National Transportation Integrated Search

2000-11-01

Four normal propyl bromide (nPB) solvents were evaluated for use as chlorinated solvent replacements in typical hot mix asphalt (HMA) extraction and recovery processes. The experimental design included one method of extraction (centrifuge), one metho...

CO{sub 2}-philic oligomers as novel solvents for CO{sub 2} absorption

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

Miller, Matthew B; Luebke, David R; Enick, Robert M

2010-01-01

Desirable properties for an oligomeric CO{sub 2}-capture solvent in an integrated gasification combined cycle (IGCC) plant include high selectivity for CO{sub 2} over H{sub 2} and water, low viscosity, low vapor pressure, low cost, and minimal environmental, health, and safety impacts. The neat solvent viscosity and solubility of CO{sub 2}, measured via bubble-point loci and presented on a pressure−composition diagram (weight basis), and water miscibility in CO{sub 2}-philic solvents have been determined and compared to results obtained with Selexol, a commercial oligomeric CO{sub 2} solvent. The solvents tested include polyethyleneglycol dimethylether (PEGDME), polypropyleneglycol dimethylether (PPGDME), polypropyleneglycol diacetate (PPGDAc), polybutyleneglycol diacetatemore » (PBGDAc), polytetramethyleneetherglycol diacetate (PTMEGDAc), glyceryl triacetate (GTA), polydimethyl siloxane (PDMS), and perfluorpolyether (PFPE) that has a perfluorinated propyleneglycol monomer unit. Overall, PDMS and PPGDME are the best oligomeric solvents tested and exhibit properties that make them very promising alternatives for the selective absorption of CO{sub 2} from a mixed gas stream, especially if the absorption of water is undesirable.« less

Inkjet printing of 2D layered materials.

PubMed

Li, Jiantong; Lemme, Max C; Östling, Mikael

2014-11-10

Inkjet printing of 2D layered materials, such as graphene and MoS2, has attracted great interests for emerging electronics. However, incompatible rheology, low concentration, severe aggregation and toxicity of solvents constitute critical challenges which hamper the manufacturing efficiency and product quality. Here, we introduce a simple and general technology concept (distillation-assisted solvent exchange) to efficiently overcome these challenges. By implementing the concept, we have demonstrated excellent jetting performance, ideal printing patterns and a variety of promising applications for inkjet printing of 2D layered materials. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Radical kinetics in sub- and supercritical carbon dioxide: thermodynamic rate tuning.

PubMed

Ghandi, Khashayar; McFadden, Ryan M L; Cormier, Philip J; Satija, Paras; Smith, Marisa

2012-06-28

We report rate constants for muonium addition to 1,1-difluoroethylene (vinylidene fluoride) in CO2 at 290-530 K, 40-360 bar, and 0.05-0.90 g cm(-3). Rate constants are mapped against their thermodynamic conditions, demonstrating the kinetic tuning ability of the solvent. The reaction exhibits critical slowing near conditions of maximum solvent isothermal compressibility, where activation volumes of unprecedentedly large magnitudes on the order of ±10(6) cm(3) mol(-1) are observed. Such values are suggestive of pressure being a significant parameter for tuning fluorolkene reactivity.

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.

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

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

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

2013-02-01

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

Organic solvent exposure and hearing loss in a cohort of aluminium workers.

PubMed

Rabinowitz, P M; Galusha, D; Slade, M D; Dixon-Ernst, C; O'Neill, A; Fiellin, M; Cullen, M R

2008-04-01

Organic solvent exposure has been shown to cause hearing loss in animals and humans. Less is known about the risk of hearing loss due to solvent exposures typically found in US industry. The authors performed a retrospective cohort study to examine the relationship between solvent exposure and hearing loss in US aluminium industry workers. A cohort of 1319 workers aged 35 years or less at inception was followed for 5 years. Linkage of employment, industrial hygiene and audiometric surveillance records allowed for estimation of noise and solvent exposures and hearing loss rates over the study period. Study subjects were classified as "solvent exposed" or not, on the basis of industrial hygiene records linked with individual job histories. High frequency hearing loss was modelled as both a continuous and a dichotomous outcome. Typical solvent exposures involved mixtures of xylene, toluene and/or methyl ethyl ketone (MEK). Recorded solvent exposure levels varied widely both within and between jobs. In a multivariate logistic model, risk factors for high frequency hearing loss included age (OR = 1.06, p = 0.004), hunting or shooting (OR = 1.35, p = 0.049), noisy hobbies (OR = 1.74, p = 0.01), baseline hearing level (OR = 1.04, p<0.001) and solvent exposure (OR = 1.87, p = 0.004). A multivariate linear regression analysis similarly found significant associations between high frequency hearing loss and age (p<0.001), hunting or shooting (p<0.001), noisy hobbies (p = 0.03), solvent exposure (p<0.001) and baseline hearing (p = 0.03). These results suggest that occupational exposure to organic solvent mixtures is a risk factor for high frequency hearing loss, although the data do not allow conclusions about dose-response relationships. Industries with solvent-exposed workers should include such workers in hearing conservation programs.

CO 2 Binding Organic Liquids Gas Capture with Polarity Swing Assisted Regeneration

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

Heldebrant, David

This report outlines the comprehensive bench-scale testing of the CO 2-binding organic liquids (CO 2BOLs) solvent platform and its unique Polarity Swing Assisted Regeneration (PSAR). This study outlines all efforts on a candidate CO 2BOL solvent molecule, including solvent synthesis, material characterization, preliminary toxicology studies, and measurement of all physical, thermodynamic and kinetic data, including bench-scale testing. Equilibrium and kinetic models and analysis were made using Aspen Plus™. Preliminary process configurations, a technoeconomic assessment and solvent performance projections for separating CO 2 from a subcritical coal-fired power plant are compared to the U.S. Department of Energy's Case 10 monoethanolamine baseline.

Effect on de-greasing solvents on conductive separable connector shields and semiconductive cable shields

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

Perry, D.D.; Bolcar, J.P.

1990-04-01

A study has been conducted to determine the effects of commercial degreasing solvents on the conductivity of an EPDM separable connector shield and two types of cable shields based on EPR and XLPE, respectively. Solvents tested included a chlorinated solvent based on 1,1,1-trichloroethane and several so-called citrus solvents consisting of the natural terpene, limonene, or blends of limonene with other hydrocarbons. All the solvents significantly degraded the conductivity of the EPR and EPDM materials, but had little effect on the XLPE cable shield. The solvents differed, however, in the extent of their effects, the rate of recovery of conductivity aftermore » removal of the solvent, and the degree to which the original conductivity of the material was restored. The consequences of these results in terms of appropriate field use of these types of solvents by utility personnel are discussed.« less

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.

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.

Process for the removal of impurities from combustion fullerenes

DOEpatents

Alford, J. Michael; Bolskar, Robert

2005-08-02

The invention generally relates to purification of carbon nanomaterials, particularly fullerenes, by removal of PAHs and other hydrocarbon impurities. The inventive process involves extracting a sample containing carbon nanomaterials with a solvent in which the PAHs are substantially soluble but in which the carbon nanomaterials are not substantially soluble. The sample can be repeatedly or continuously extracted with one or more solvents to remove a greater amount of impurities. Preferred solvents include ethanol, diethyl ether, and acetone. The invention also provides a process for efficiently separating solvent extractable fullerenes from samples containing fullerenes and PAHs wherein the sample is extracted with a solvent in which both fullerenes and PAHs are substantially soluble and the sample extract then undergoes selective extraction to remove PAHs. Suitable solvents in which both fullerenes and PAHs are soluble include o-xylene, toluene, and o-dichlorobenzene. The purification process is capable of treating quantities of combustion soot in excess of one kilogram and can produce fullerenes or fullerenic soot of suitable purity for many applications.

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.

Cleaning painted surfaces: evaluation of leaching phenomenon induced by solvents applied for the removal of gel residues.

PubMed

Casoli, Antonella; Di Diego, Zaira; Isca, Clelia

2014-12-01

Cleaning is one of the most important, delicate, and at the same time controversial processes in the conservation treatment of paintings. Although a strict definition of cleaning would be the removal of dirt, grime, or other accretions (surface cleaning), in the conservation field, cleaning is used in the broader meaning to include thinning/removing altered or “unwanted layers” of materials without damaging or altering the physicochemical properties of the surfaces to be preserved. The cleaning of unvarnished paintings is one of the most critical issues that are currently discussed. Several studies exist regarding different cleaning tools, such as gels, soaps, enzymes, ionic liquids, and foams, as well as various dry methods and lasers, but only a few have been performed on the risk associated with the use of water and organic solvents for the cleaning treatments in relation to the original paint binder. The aim of the study is to verify analytically the behavior of water gelling agents during cleaning treatments and the interaction of the following elements: water or organic solvents applied for the removal of gel residues with the original lipid paint binder. For this purpose, the study was conducted on a fragment of canvas painting (sixteenth to seventeenth century) of Soprintendenza per i Beni Storici, Artistici ed Etnoantropologici del Friuli Venezia Giulia (Superintendence for the Historical, Artistic and Ethno-anthropological Heritage of Friuli Venezia Giulia), Udine by means of Fourier transform infrared spectroscopy, gas chromatography/mass spectrometry, and scanning electron microscopy.

Palladium-catalyzed hydrodehalogenation of 1,2,4,5-tetrachlorobenzene in water-ethanol mixtures.

PubMed

Wee, Hun-Young; Cunningham, Jeffrey A

2008-06-30

Palladium-catalyzed hydrodehalogenation (HDH) was applied for destroying 1,2,4,5-tetrachlorobenzene (TeCB) in mixtures of water and ethanol. This investigation was performed as a critical step in the development of a new technology for clean-up of soil contaminated by halogenated hydrophobic organic contaminants. The main goals of the investigation were to demonstrate the feasibility of the technology, to determine the effect of the solvent composition (water:ethanol ratio), and to develop a model for the kinetics of the dehalogenation process. All experiments were conducted in a batch reactor at ambient temperature under mild hydrogen pressure. The experimental results are all consistent with a Langmuir-Hinshelwood model for heterogeneous catalysis. Major findings that can be interpreted within the Langmuir-Hinshelwood framework include: (1) the rate of hydrodehalogenation depends strongly on the solvent composition, increasing as the water fraction of the solvent increases; (2) the HDH rate increases as the catalyst concentration in the reactor increases; (3) when enough catalyst is present, the HDH reaction appears to follow first-order kinetics, but the kinetics appear to be zero-order at low catalyst concentrations. TeCB is converted rapidly and quantitatively to benzene, with only trace concentrations of 1,2,4-trichlorobenzene appearing as a reactive intermediate. The results obtained here have important implications for the further development of the proposed soil remediation technology, and may also be important for the treatment of other hazardous waste streams.

Laboratory Evaluation of Drop-in Solvent Alternatives to n-Propyl Bromide for Vapor Degreasing

NASA Technical Reports Server (NTRS)

Mitchell, Mark A.; Lowrey, Nikki M.

2012-01-01

Based on this limited laboratory study, solvent blends of trans-1,2 dichloroethylene with HFEs, HFCs, or PFCs appear to be viable alternatives to n-propyl bromide for vapor degreasing. The lower boiling points of these blends may lead to greater solvent loss during use. Additional factors must be considered when selecting a solvent substitute, including stability over time, VOC, GWP, toxicity, and business considerations.

Process for removing halogenated aliphatic and aromatic compounds from petroleum products

DOEpatents

Googin, J.M.; Napier, J.M.; Travaglini, M.A.

1983-09-20

A process is described for removing halogenated aliphatic and aromatic compounds, e.g., polychlorinated biphenyls, from petroleum products by solvent extraction. The halogenated aliphatic and aromatic compounds are extracted from a petroleum product into a polar solvent by contacting the petroleum product with the polar solvent. The polar solvent is characterized by a high solubility for the extracted halogenated aliphatic and aromatic compounds, a low solubility for the petroleum product and considerable solvent power for polyhydroxy compound. The preferred polar solvent is dimethylformamide. A miscible compound, such as, water or a polyhydroxy compound, is added to the polar extraction solvent to increase the polarity of the polar extraction solvent. The halogenated aliphatic and aromatic compounds are extracted from the highly-polarized mixture of water or polyhydroxy compound and polar extraction solvent into a low polar or nonpolar solvent by contacting the water or polyhydroxy compound-polar solvent mixture with the low polar or nonpolar solvent. The halogenated aliphatic and aromatic compounds and the low polar or nonpolar solvent are separated by physical means, e.g., vacuum evaporation. The polar and nonpolar solvents are recovered from recycling. The process can easily be designed for continuous operation. Advantages of the process include that the polar solvent and a major portion of the nonpolar solvent can be recycled, the petroleum products are reclaimable and the cost for disposing of waste containing polychlorinated biphenyls is significantly reduced. 1 fig.

Process for removing halogenated aliphatic and aromatic compounds from petroleum products

DOEpatents

Googin, John M.; Napier, John M.; Travaglini, Michael A.

1983-01-01

A process for removing halogenated aliphatic and aromatic compounds, e.g., polychlorinated biphenyls, from petroleum products by solvent extraction. The halogenated aliphatic and aromatic compounds are extracted from a petroleum product into a polar solvent by contacting the petroleum product with the polar solvent. The polar solvent is characterized by a high solubility for the extracted halogenated aliphatic and aromatic compounds, a low solubility for the petroleum product and considerable solvent power for polyhydroxy compound. The preferred polar solvent is dimethylformamide. A miscible compound, such as, water or a polyhydroxy compound, is added to the polar extraction solvent to increase the polarity of the polar extraction solvent. The halogenated aliphatic and aromatic compounds are extracted from the highly-polarized mixture of water or polyhydroxy compound and polar extraction solvent into a low polar or nonpolar solvent by contacting the water or polyhydroxy compound-polar solvent mixture with the low polar or nonpolar solvent. The halogenated aliphatic and aromatic compounds and the low polar or nonpolar solvent are separated by physical means, e.g., vacuum evaporation. The polar and nonpolar solvents are recovered from recycling. The process can easily be designed for continuous operation. Advantages of the process include that the polar solvent and a major portion of the nonpolar solvent can be recycled, the petroleum products are reclaimable and the cost for disposing of waste containing polychlorinated biphenyls is significantly reduced.

Process for removing halogenated aliphatic and aromatic compounds from petroleum products. [Polychlorinated biphenyls; methylene chloride; perchloroethylene; trichlorofluoroethane; trichloroethylene; chlorobenzene

DOEpatents

Googin, J.M.; Napier, J.M.; Travaglini, M.A.

1982-03-31

A process for removing halogenated aliphatic and aromatic compounds, e.g., polychlorinated biphenyls, from petroleum products by solvent extraction. The halogenated aliphatic and aromatic compounds are extracted from a petroleum product into a polar solvent by contracting the petroleum product with the polar solvent. The polar solvent is characterized by a high solubility for the extracted halogenated aliphatic and aromatic compounds, a low solubility for the petroleum product and considerable solvent power for polyhydroxy compound. The preferred polar solvent is dimethylformamide. A miscible polyhydroxy compound, such as, water, is added to the polar extraction solvent to increase the polarity of the polar extraction solvent. The halogenated aliphatic and aromatic compounds are extracted from the highly-polarized mixture of polyhydroxy compound and polar extraction solvent into a low polar or nonpolar solvent by contacting the polyhydroxy compound-polar solvent mixture with the low polar or nonpolar solvent. The halogenated aliphatic and aromatic compounds in the low polar or nonpolar solvent by physical means, e.g., vacuum evaporation. The polar and nonpolar solvents are recovered for recycling. The process can easily be designed for continuous operation. Advantages of the process include that the polar solvent and a major portion of the nonpolar solvent can be recycled, the petroleum products are reclaimable and the cost for disposing of waste containing polychlorinated biphenyls is significantly reduced. 2 tables.

Solvent-coordinate free-energy landscape view of water-mediated ion-pair dissociation

NASA Astrophysics Data System (ADS)

Yonetani, Yoshiteru

2017-12-01

Water-mediated ion-pair dissociation is studied by molecular dynamics simulations of NaCl in water. Multidimensional free-energy analysis clarifies the relation between two essential solvent coordinates: the water coordination number and water-bridge formation. These two are related in a complex way. Both are necessary to describe ion-pair dissociation. The mechanism constructed with both solvent variables clearly shows the individual roles. The water coordination number is critical for starting ion-pair dissociation. Water-bridge formation is also important because it increases the likelihood of ion-pair dissociation by reducing the dissociation free-energy barrier. Additional Ca-Cl and NH4-Cl calculations show that these conclusions are unaffected by changes in the ion charge and shape. The present results will contribute to future explorations of many other molecular events such as surface water exchange and protein-ligand dissociation because the same mechanism is involved in such events.

X-ray photoelectron spectroscopy study of para-substituted benzoic acids chemisorbed to aluminum oxide thin films

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

Kreil, Justin; Ellingsworth, Edward; Szulczewski, Greg

A series of para-substituted, halogenated (F, Cl, Br, and I) benzoic acid monolayers were prepared on the native oxide of aluminum surfaces by solution self-assembly and spin-coating techniques. The monolayers were characterized by x-ray photoelectron spectroscopy (XPS) and water contact angles. Several general trends are apparent. First, the polarity of the solvent is critical to monolayer formation. Protic polar solvents produced low coverage monolayers; in contrast, nonpolar solvents produced higher coverage monolayers. Second, solution deposition yields a higher surface coverage than spin coating. Third, the thickness of the monolayers determined from XPS suggests the plane of the aromatic ring ismore » perpendicular to the surface with the carboxylate functional group most likely binding in a bidentate chelating geometry. Fourth, the saturation coverage (∼2.7 × 10{sup 14} molecules cm{sup −2}) is independent of the para-substituent.« less

Headspace profiling of cocaine samples for intelligence purposes.

PubMed

Dujourdy, Laurence; Besacier, Fabrice

2008-08-06

A method for determination of residual solvents in illicit hydrochloride cocaine samples using static headspace-gas chromatography (HS-GC) associated with a storage computerized procedure is described for the profiling and comparison of seizures. The system involves a gas chromatographic separation of 18 occluded solvents followed by fully automatic data analysis and transfer to a PHP/MySQL database. First, a fractional factorial design was used to evaluate the main effects of some critical method parameters (salt choice, vial agitation intensity, oven temperature, pressurization and loop equilibration) on the results with a minimum of experiments. The method was then validated for tactical intelligence purposes (batch comparison) via several studies: selection of solvents and mathematical comparison tool, reproducibility and "cutting" influence studies. The decision threshold to determine the similarity of two samples was set and false positives and negatives evaluated. Finally, application of the method to distinguish geographical origins is discussed.

Electrodeposition of metals from supercritical fluids

PubMed Central

Ke, Jie; Su, Wenta; Howdle, Steven M.; George, Michael W.; Cook, David; Perdjon-Abel, Magda; Bartlett, Philip N.; Zhang, Wenjian; Cheng, Fei; Levason, William; Reid, Gillian; Hyde, Jason; Wilson, James; Smith, David C.; Mallik, Kanad; Sazio, Pier

2009-01-01

Electrodeposition is a widely used materials-deposition technology with a number of unique features, in particular, the efficient use of starting materials, conformal, and directed coating. The properties of the solvent medium for electrodeposition are critical to the technique's applicability. Supercritical fluids are unique solvents which give a wide range of advantages for chemistry in general, and materials processing in particular. However, a widely applicable approach to electrodeposition from supercritical fluids has not yet been developed. We present here a method that allows electrodeposition of a range of metals from supercritical carbon dioxide, using acetonitrile as a co-solvent and supercritical difluoromethane. This method is based on a careful selection of reagent and supporting electrolyte. There are no obvious barriers preventing this method being applied to deposit a range of materials from many different supercritical fluids. We present the deposition of 3-nm diameter nanowires in mesoporous silica templates using this methodology. PMID:19706479

Solvent-free melting techniques for the preparation of lipid-based solid oral formulations.

PubMed

Becker, Karin; Salar-Behzadi, Sharareh; Zimmer, Andreas

2015-05-01

Lipid excipients are applied for numerous purposes such as taste masking, controlled release, improvement of swallowability and moisture protection. Several melting techniques have evolved in the last decades. Common examples are melt coating, melt granulation and melt extrusion. The required equipment ranges from ordinary glass beakers for lab scale up to large machines such as fluid bed coaters, spray dryers or extruders. This allows for upscaling to pilot or production scale. Solvent free melt processing provides a cost-effective, time-saving and eco-friendly method for the food and pharmaceutical industries. This review intends to give a critical overview of the published literature on experiences, formulations and challenges and to show possibilities for future developments in this promising field. Moreover, it should serve as a guide for selecting the best excipients and manufacturing techniques for the development of a product with specific properties using solvent free melt processing.

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

Xu, Wu; Xiao, Jie; Zhang, Jian

The selection and optimization of non-aqueous electrolytes for ambient operations of lithium/air batteries has been studied. Organic solvents with low volatility and low moisture absorption are necessary to minimize the change of electrolyte compositions and the reaction between lithium anode and water during discharge process. It is critical to make the electrolytes with high polarity so that it can reduce wetting and flooding of carbon based air electrode and lead to improved battery performance. For ambient operations, the viscosity, ionic conductivity, and oxygen solubility of the electrolyte are less important than the polarity of organic solvents once the electrolyte hasmore » reasonable viscosity, conductivity, and oxygen solubility. It has been found that PC/EC mixture is the best solvent system and LiTFSI is the most feasible salt for ambient operations of Li/air batteries. Battery performance is not very sensitive to PC/EC ratio or salt concentration.« less

Developmental toxicity of prenatal exposure to toluene.

PubMed

Bowen, Scott E; Hannigan, John H

2006-01-01

Organic solvents have become ubiquitous in our environment and are essential for industry. Many women of reproductive age are increasingly exposed to solvents such as toluene in occupational settings (ie, long-term, low-concentration exposures) or through inhalant abuse (eg, episodic, binge exposures to high concentrations). The risk for teratogenic outcome is much less with low to moderate occupational solvent exposure compared with the greater potential for adverse pregnancy outcomes, developmental delays, and neurobehavioral problems in children born to women exposed to high concentrations of abused organic solvents such as toluene, 1,1,1-trichloroethane, xylenes, and nitrous oxide. Yet the teratogenic effects of abuse patterns of exposure to toluene and other inhalants remain understudied. We briefly review how animal models can aid substantially in clarifying the developmental risk of exposure to solvents for adverse biobehavioral outcomes following abuse patterns of use and in the absence of associated health problems and co-drug abuse (eg, alcohol). Our studies also begin to establish the importance of dose (concentration) and critical perinatal periods of exposure to specific outcomes. The present results with our clinically relevant animal model of repeated, brief, high-concentration binge prenatal toluene exposure demonstrate the dose-dependent effect of toluene on prenatal development, early postnatal maturation, spontaneous exploration, and amphetamine-induced locomotor activity. The results imply that abuse patterns of toluene exposure may be more deleterious than typical occupational exposure on fetal development and suggest that animal models are effective in studying the mechanisms and risk factors of organic solvent teratogenicity.

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.

Synthesis of soluble conducting polymers by acoustic mixing

DOEpatents

Kane, Marie C.

2016-09-13

A method including combining an aniline monomer, an oxidant, water and an organic solvent; subjecting the combination to acoustic mixing to form an emulsion; and recovering a polyaniliine from the combination. A method including combining a aniline monomer, an oxidant, water and an organic solvent; forming a polyaniline by acoustic mixing the combination; and recovering the polyaniliine from the combination. A method including forming a combination of an aniline monomer, an oxidant, water and an organic solvent in the absence of an emulsifier; acoustic mixing the combination for a time period to form a polyaniline; and recovering a polyaniliine from the combination.

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.

Halogenated solvent remediation

DOEpatents

Sorenson, Kent S.

2004-08-31

Methods for enhancing bioremediation of ground water contaminated with nonaqueous halogenated solvents are disclosed. A preferred method includes adding a composition to the ground water wherein the composition is an electron donor for microbe-mediated reductive dehalogenation of the halogenated solvents and enhances mass transfer of the halogenated solvents from residual source areas into the aqueous phase of the ground water. Illustrative compositions effective in these methods include surfactants such as C.sub.2 -C.sub.4 carboxylic acids and hydroxy acids, salts thereof, esters of C.sub.2 -C.sub.4 carboxylic acids and hydroxy acids, and mixtures thereof. Especially preferred compositions for use in these methods include lactic acid, salts of lactic acid, such as sodium lactate, lactate esters, and mixtures thereof. The microbes are either indigenous to the ground water, or such microbes can be added to the ground water in addition to the composition.

Recovery of Palm Oil and Valuable Material from Oil Palm Empty Fruit Bunch by Sub-critical Water.

PubMed

Ahmad Kurnin, Nor Azrin; Shah Ismail, Mohd Halim; Yoshida, Hiroyuki; Izhar, Shamsul

2016-01-01

Oil palm empty fruit bunch (EFB) is one of the solid wastes produced in huge volume by palm oil mill. Whilst it still contains valuable oil, approximately 22.6 million tons is generated annually and treated as solid waste. In this work, sub-critical water (sub-cw) was used to extract oil, sugar and tar from spikelet of EFB. The spikelet was treated with sub-cw between 180-280°C and a reaction time of 2 and 5 minutes. The highest yield of oil was 0.075 g-oil/g-dry EFB, obtained at 240°C and reaction time of 5 minutes. Astonishingly, oil that was extracted through this method was 84.5% of that obtained through Soxhlet method using hexane. Yield of oil extracted was strongly affected by the reaction temperature and time. Higher reaction temperature induces the dielectric constant of water towards the non-polar properties of solvent; thus increases the oil extraction capability. Meanwhile, the highest yield of sugar was 0.20 g-sugar/g-dry EFB obtained at 220°C. At this temperature, the ion product of water is high enough to enable maximum sub-critical water hydrolysis reaction. This study showed that oil and other valuable material can be recovered using water at sub-critical condition, and most attractive without the use of harmful organic solvent.

Apparatus and method for reprocessing and separating spent nuclear fuels. [Patent application

DOEpatents

Krikorian, O.H.; Grens, J.Z.; Parrish, W.H. Sr.

1982-01-19

Spent nuclear fuels, including actinide fuels, volatile and non-volatile fission products, are reprocessed and separated in a molten metal solvent housed in the reaction region of a separation vessel which includes a reflux region positioned above the molten tin solvent. The reflux region minimizes loss of evaporated solvent during the separation of the actinide fuels from the volatile fission products. Additionally, inclusion of the reflux region permits the separation of the more volatile fission products (noncondensable) from the less volatile ones (condensable).

Method and solvent composition for regenerating an ion exchange resin

DOEpatents

Even, William R.; Irvin, David J.; Irvin, Jennifer A.; Tarver, Edward E.; Brown, Gilbert M.; Wang, James C. F.

2002-01-01

A method and composition for removing perchlorate from a highly selective ion exchange resin is disclosed. The disclosed approach comprises treating the resin in a solution of super critical or liquid carbon dioxide and one or more quaternary ammonium chloride surfactant compounds.

Permeability of starch gel matrices and select films to solvent vapors

USDA-ARS?s Scientific Manuscript database

The controlled release of volatile, agrochemicals is critical in developing approaches to pest control that are economically viable and environmentally sound. Dispensing systems that are made of materials that degrade in agricultural environments when they are spent offer distinct advantages over no...

Homochiral stereochemistry: the missing link of structure to energetics in protein folding.

PubMed

Kumar, Anil; Ramakrishnan, Vibin; Ranbhor, Ranjit; Patel, Kirti; Durani, Susheel

2009-12-24

The notion is tested that homochiral stereochemistry being ubiquitous to protein structure could be critical to protein folding as well, causing it to become frustrated energetically providing the basis for its solvent- and sequence-mediated control. The proof in support of the notion is found in a consensus of experiment and computation according to which suitable oligopeptides are in their folding-unfolding equilibria, at both macrostate and microstate levels, susceptible to dielectric because of the conflict of peptide-chain electrostatics with interpeptide hydrogen bonds when the structure is poly-L but not when it is alternating-L,D. The argument is thus made that homochiral stereochemistry may in protein folding provide the unifying basis for its solvent- and sequence-mediated control based on screening of peptide-chain electrostatics under conflict with folding of the chain due to homochiral stereochemistry. Dielectric is brought into spotlight as the effect comparatively obscure but presumably critical to the folding in protein structure for its control.

Scaling and self-organized criticality in proteins: Lysozyme c

NASA Astrophysics Data System (ADS)

Phillips, J. C.

2009-11-01

Proteins appear to be the most dramatic natural example of self-organized criticality (SOC), a concept that explains many otherwise apparently unlikely phenomena. Protein functionality is often dominated by long-range hydro(phobic/philic) interactions, which both drive protein compaction and mediate protein-protein interactions. In contrast to previous reductionist short-range hydrophobicity scales, the holistic Moret-Zebende hydrophobicity scale [Phys. Rev. E 75, 011920 (2007)] represents a hydroanalytic tool that bioinformatically quantifies SOC in a way fully compatible with evolution. Hydroprofiling identifies chemical trends in the activities and substrate binding abilities of model enzymes and antibiotic animal lysozymes c , as well as defensins, which have been the subject of tens of thousands of experimental studies. The analysis is simple and easily performed and immediately yields insights not obtainable by traditional methods based on short-range real-space interactions, as described either by classical force fields used in molecular-dynamics simulations, or hydrophobicity scales based on transference energies from water to organic solvents or solvent-accessible areas.

Liquid precursor inks for deposition of In--Se, Ga--Se and In--Ga--Se

DOEpatents

Curtis, Calvin J.; Hersh, Peter A.; Miedaner, Alexander; Habas, Susan; van Hest, Maikel; Ginley, David S.

2015-08-11

An ink includes a solution of selenium in ethylene diamine solvent and a solution of at least one metal salt selected from the group consisting of an indium salt or a gallium salt in at least one solvent including an organic amide. The organic amide can include dimethylformamide. The organic amide can include N-methylpyrrolidone.

Natural deep eutectic solvents as eco-friendly and sustainable dilution medium for the determination of residual organic solvents in pharmaceuticals with static headspace-gas chromatography.

PubMed

Wang, Meilian; Fang, Sheng; Liang, Xianrui

2018-06-04

Reported here is a simple and rapid static headspace gas chromatography (SHS-GC) method for the determination of trace solvents including ethanol, isopropanol, n-butanol, 1,4-dioxane, tetrahydrofuran, acetonitrile, methanol and acetone which commonly used in drug production process. Natural deep eutectic solvents (NADESs) are firstly used as the matrix medium for this method, which provided high sensitivity for residual solvents detection. With the optimized method, validation experiments were performed and the data showed excellent linearity for all the solvents (R 2 ≥ 0.999, n = 7). The limits of detection (LOD) for ethanol, isopropanol, n-butanol, 1,4-dioxane, tetrahydrofuran, acetonitrile, methanol and acetone are 0.09, 0.08, 0.07, 0.11, 0.06, 0.10, 0.12 and 0.08 μg g -1 , respectively. Accuracy was checked by a recovery experiment at three different levels, and the recoveries of the tested solvents were ranged from 94.3% to 105.4%. The relative standard deviation (RSD) of each solvent for intra- and inter-day precision is in the range of 0.85 to 3.65 and 1.51 to 4.53, respectively. The developed approach can be readily used for determination of the residual solvents in six active pharmaceutical ingredients including pramipexole dihydrochloride, rivaroxaban, lisinopril, ramipril, imatinib mesylate and sitagliptin. Copyright © 2018 Elsevier B.V. All rights reserved.

Theory of Metastable State Relaxation for Non-Critical Binary Systems with Non-Conserved Order Parameter

NASA Technical Reports Server (NTRS)

Izmailov, Alexander; Myerson, Allan S.

1993-01-01

A new mathematical ansatz for a solution of the time-dependent Ginzburg-Landau non-linear partial differential equation is developed for non-critical systems such as non-critical binary solutions (solute + solvent) described by the non-conserved scalar order parameter. It is demonstrated that in such systems metastability initiates heterogeneous solute redistribution which results in formation of the non-equilibrium singly-periodic spatial solute structure. It is found how the time-dependent period of this structure evolves in time. In addition, the critical radius r(sub c) for solute embryo of the new solute rich phase together with the metastable state lifetime t(sub c) are determined analytically and analyzed.

The secondary drying and the fate of organic solvents for spray dried dispersion drug product.

PubMed

Hsieh, Daniel S; Yue, Hongfei; Nicholson, Sarah J; Roberts, Daniel; Schild, Richard; Gamble, John F; Lindrud, Mark

2015-05-01

To understand the mechanisms of secondary drying of spray-dried dispersion (SDD) drug product and establish a model to describe the fate of organic solvents in such a product. The experimental approach includes characterization of the SDD particles, drying studies of SDD using an integrated weighing balance and mass spectrometer, and the subsequent generation of the drying curve. The theoretical approach includes the establishment of a Fickian diffusion model. The kinetics of solvent removal during secondary drying from the lab scale to a bench scale follows Fickian diffusion model. Excellent agreement is obtained between the experimental data and the prediction from the modeling. The diffusion process is dependent upon temperature. The key to a successful scale up of the secondary drying is to control the drying temperature. The fate of primary solvents including methanol and acetone, and their potential impurity such as benzene can be described by the Fickian diffusion model. A mathematical relationship based upon the ratio of diffusion coefficient was established to predict the benzene concentration from the fate of the primary solvent during the secondary drying process.

Formulating Precursors for Coating Metals and Ceramics

NASA Technical Reports Server (NTRS)

Morales, Wilfredo; Gatica, Jorge E.; Reye, John T.

2005-01-01

A protocol has been devised for formulating low-vapor-pressure precursors for protective and conversion coatings on metallic and ceramic substrates. The ingredients of a precursor to which the protocol applies include additives with phosphate esters, or aryl phosphate esters in solution. Additives can include iron, chromium, and/or other transition metals. Alternative or additional additives can include magnesium compounds to facilitate growth of films on substrates that do not contain magnesium. Formulation of a precursor begins with mixing of the ingredients into a high-vapor-pressure solvent to form a homogeneous solution. Then the solvent is extracted from the solution by evaporation - aided, if necessary, by vacuum and/or slight heating. The solvent is deemed to be completely extracted when the viscosity of the remaining solution closely resembles the viscosity of the phosphate ester or aryl phosphate ester. In addition, satisfactory removal of the solvent can be verified by means of a differential scanning calorimetry essay: the absence of endothermic processes for temperatures below 150 C would indicate that the residual solvent has been eliminated from the solution beyond a detectable dilution level.

Thermodynamic of cellulose solvation in novel solvent mixtures

NASA Astrophysics Data System (ADS)

Das, Ritankar; Chu, Jhih-Wei

2013-04-01

Biomass contains abundant amounts of cellulose as crystalline microfibrils. A limiting step to using cellulose as an alternative energy source, however, is the hydrolysis of the biomass and subsequent transformation into fuels. Cellulose is insoluble in most solvents including organic solvents and water, but it is soluble in some ionic liquids like BMIM-Cl. This project aims to find alternative solvents that are less expensive and are more environmentally benign than the ionic liquids. All-atom molecular dynamics simulations were performed on dissociated glucan chains separated by multiple (4-5) solvation shells, in the presence of several novel solvents and solvent mixtures. The solubility of the chains in each solvent was indicated by contacts calculations after the equilibration of the molecular dynamics. It was discovered that pyridine and imidazole acted as the best solvents because their aromatic electronic structure was able to effectively disrupt the inter-sheet interactions among the glucan chains in the axial direction, and because perturbation of the solvent interactions in the presence of glucan chains was minimal.

Thermodynamic of cellulose solvation in novel solvent mixtures

NASA Astrophysics Data System (ADS)

Das, Ritankar

2013-03-01

Biomass contains abundant amounts of cellulose as crystalline microfibrils. A limiting step to using cellulose as an alternative energy source, however, is the hydrolysis of the biomass and subsequent transformation into fuels. Cellulose is insoluble in most solvents including organic solvents and water, but it is soluble in some ionic liquids like BMIM-Cl. This project aims to find alternative solvents that are less expensive and are more environmentally benign than the ionic liquids. All-atom molecular dynamics simulations were performed on dissociated glucan chains separated by multiple (4-5) solvation shells, in the presence of several novel solvents and solvent mixtures. The solubility of the chains in each solvent was indicated by contacts calculations after the equilibration of the molecular dynamics. It was discovered that pyridine and imidazole acted as the best solvents because their aromatic electronic structure was able to effectively disrupt the inter-sheet interactions among the glucan chains in the axial direction, and because perturbation of the solvent interactions in the presence of glucan chains was minimal.

Thermodynamics of cellulose solvation in novel solvent mixtures

NASA Astrophysics Data System (ADS)

Das, Ritankar; Chu, Jhih-Wei

2012-10-01

Biomass contains abundant amounts of cellulose as crystalline microfibrils. A limiting step to using cellulose as an alternative energy source, however, is the hydrolysis of the biomass and subsequent transformation into fuels. Cellulose is insoluble in most solvents including organic solvents and water, but it is soluble in some ionic liquids like BMIM-Cl. This project aims to find alternative solvents that are less expensive and are more environmentally benign than the ionic liquids. All-atom molecular dynamics simulations were performed on dissociated glucan chains separated by multiple (4-5) solvation shells, in the presence of several novel solvents and solvent mixtures. The solubility of the chains in each solvent was indicated by contacts calculations after the equilibration of the molecular dynamics. It was discovered that pyridine and imidazole acted as the best solvents because their aromatic electronic structure was able to effectively disrupt the inter-sheet interactions among the glucan chains in the axial direction, and because perturbation of the solvent interactions in the presence of glucan chains was minimal.

Thermodynamic of cellulose solvation in novel solvent mixtures

NASA Astrophysics Data System (ADS)

Das, Ritankar

2012-11-01

Biomass contains abundant amounts of cellulose as crystalline microfibrils. A limiting step to using cellulose as an alternative energy source, however, is the hydrolysis of the biomass and subsequent transformation into fuels. Cellulose is insoluble in most solvents including organic solvents and water, but it is soluble in some ionic liquids like BMIM-Cl. This project aims to find alternative solvents that are less expensive and are more environmentally benign than the ionic liquids. All-atom molecular dynamics simulations were performed on dissociated glucan chains separated by multiple (4-5) solvation shells, in the presence of several novel solvents and solvent mixtures. The solubility of the chains in each solvent was indicated by contacts calculations after the equilibration of the molecular dynamics. It was discovered that pyridine and imidazole acted as the best solvents because their aromatic electronic structure was able to effectively disrupt the inter-sheet interactions among the glucan chains in the axial direction, and because perturbation of the solvent interactions in the presence of glucan chains was minimal.

Microbial process for the preparation of acetic acid, as well as solvent for its extraction from the fermentation broth

DOEpatents

Gaddy, James L.; Clausen, Edgar C.; Ko, Ching-Whan; Wade, Leslie E.; Wikstrom, Carl V.

2007-03-27

A modified water-immiscible solvent useful in the extraction of acetic acid from aqueous streams is a substantially pure mixture of isomers of highly branched di-alkyl amines. Solvent mixtures formed of such a modified solvent with a desired co-solvent, preferably a low boiling hydrocarbon, are useful in the extraction of acetic acid from aqueous gaseous streams. An anaerobic microbial fermentation process for the production of acetic acid employs such solvents, under conditions which limit amide formation by the solvent and thus increase the efficiency of acetic acid recovery. Methods for the direct extraction of acetic acid and the extractive fermentation of acetic acid also employ the modified solvents and increase efficiency of acetic acid production. Such increases in efficiency are also obtained where the energy source for the microbial fermentation contains carbon dioxide and the method includes a carbon dioxide stripping step prior to extraction of acetic acid in solvent.

Microbial process for the preparation of acetic acid, as well as solvent for its extraction from the fermentation broth

DOEpatents

Gaddy, James L.; Clausen, Edgar C.; Ko, Ching-Whan; Wade, Leslie E.; Wikstrom, Carl V.

2004-06-22

A modified water-immiscible solvent useful in the extraction of acetic acid from aqueous streams is a substantially pure mixture of isomers of highly branched di-alkyl amines. Solvent mixtures formed of such a modified solvent with a desired co-solvent, preferably a low boiling hydrocarbon, are useful in the extraction of acetic acid from aqueous gaseous streams. An anaerobic microbial fermentation process for the production of acetic acid employs such solvents, under conditions which limit amide formation by the solvent and thus increase the efficiency of acetic acid recovery. Methods for the direct extraction of acetic acid and the extractive fermentation of acetic acid also employ the modified solvents and increase efficiency of acetic acid production. Such increases in efficiency are also obtained where the energy source for the microbial fermentation contains carbon dioxide and the method includes a carbon dioxide stripping step prior to extraction of acetic acid in solvent.

Probing Contaminant Transport to and from Clay Surfaces in Organic Solvents and Water Using Solution Calorimetry.

PubMed

Pourmohammadbagher, Amin; Shaw, John M

2015-09-15

Clays, in tailings, are a significant ongoing environmental concern in the mining and oilsands production industries, and clay rehabilitation following contamination poses challenges episodically. Understanding the fundamentals of clay behavior can lead to better environmental impact mitigation strategies. Systematic calorimetric measurements are shown to provide a framework for parsing the synergistic and antagonistic impacts of trace (i.e., parts per million level) components on the surface compositions of clays. The enthalpy of solution of as-received and "contaminated" clays, in as-received and "contaminated" organic solvents and water, at 60 °C and atmospheric pressure, provides important illustrative examples. Clay contamination included pre-saturation of clays with water and organic liquids. Solvent contamination included the addition of trace water to organic solvents and trace organic liquids to water. Enthalpy of solution outcomes are interpreted using a quantitative mass and energy balance modeling framework that isolates terms for solvent and trace contaminant sorption/desorption and surface energy effects. Underlying surface energies are shown to dominate the energetics of the solvent-clay interaction, and organic liquids as solvents or as trace contaminants are shown to displace water from as-received clay surfaces. This approach can be readily extended to include pH, salts, or other effects and is expected to provide mechanistic and quantitative insights underlying the stability of clays in tailings ponds and the behaviors of clays in diverse industrial and natural environments.

Homogeneity of gels and gel-derived glasses

NASA Technical Reports Server (NTRS)

Mukherjee, S. P.

1984-01-01

The significance and implications of gel preparation procedures in controlling the homogeneity of multicomponent oxide gels are discussed. The role of physicochemical factors such as the structure and chemical reactivities of alkoxides, the formation of double-metal alkoxides, and the nature of solvent(s) are critically analyzed in the context of homogeneity of gels during gelation. Three procedures for preparing gels in the SiO2-B2O3-Na2O system are examined in the context of cation distribution. Light scattering results for glasses in the SiO2-B2O3-Na2O system prepared by both the gel technique and the conventional technique are examined.

Issues Related to Cleaning Complex Geometry Surfaces with ODC-Free Solvents

NASA Technical Reports Server (NTRS)

Bradford, Blake F.; Wurth, Laura A.; Nayate, Pramod D.; McCool, Alex (Technical Monitor)

2001-01-01

Implementing ozone depleting chemicals (ODC)-free solvents into full-scale reusable solid rocket motor cleaning operations has presented problems due to the low vapor pressures of the solvents. Because of slow evaporation, solvent retention is a problem on porous substrates or on surfaces with irregular geometry, such as threaded boltholes, leak check ports, and nozzle backfill joints. The new solvents are being evaluated to replace 1,1,1-trichloroethane, which readily evaporates from these surfaces. Selection of the solvents to be evaluated on full-scale hardware was made based on results of subscale tests performed with flat surface coupons, which did not manifest the problem. Test efforts have been undertaken to address concerns with the slow-evaporating solvents. These concerns include effects on materials due to long-term exposure to solvent, potential migration from bolthole threads to seal surfaces, and effects on bolt loading due to solvent retention in threads. Tests performed to date have verified that retained solvent does not affect materials or hardware performance. Process modifications have also been developed to assist drying, and these can be implemented if additional drying becomes necessary.

Study on the strategies of waste solvent minimization in automobile production industry

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

Chang, C.T.; Lin, K.L.; Wu, Y.P.

1998-12-31

There are six automobile manufacturers who produce several kinds of vehicles in Taiwan. To meet the consumer`s needs, the automobile coating processes are necessary for the basic functions of anti-rust protection, weatherproofing and appearance. Some kinds of solvents are added as thinners and additives to avoid excessive viscosity of the coating materials and to increase facility productivity. The total consumption of volatile organic solvents is about 407,000 ton/year of which about 100,700 ton/year is used in surface coating. It is worthy of attention that solvents used in automobile industries account for 7,200 ton/year in major coating processes, including electrodeposition coating,more » primer coating, top coating, and bar coating, according to statistics of VOCs emission rate calculated from the data of consumption provided by each automobile plant. The amount of solvents used for washing spray gun and base coating are about 3,350 ton/year; and about 1,700 ton/year for primer coat and clear coat. The species of organic solvents include toluene, xylene, ethylacetate, n-butyl acetate, ketone, etc. VOCs emission factor from each plant lies between 500 to 650 g-VOCs/L coating. To reduce the amount of coating and waste liquor, the suggested methods include increasing gun spray efficiency, lengthening same colors painting period, reducing the solvent content in paint, and adding treatment equipment. The high solid content painting, waterborne coat, and powder coat should be used for traditional painting. Additionally, a carbon adsorption bed and zeolite rotator recovery system can replace scrubbers since they can be used as solvent recovery equipment.« less

Mass transfer in supercritical fluids instancing selected fluids in supercritical carbon dioxide

NASA Astrophysics Data System (ADS)

Hu, Miao; Benning, Rainer; Delgado, Antonio; Ertunc, Oezguer

The research interests lie in a deeper understanding of the mechanisms of diffusion and nucle-ation of organic solutes in near-and supercritical state of a solvent, which count as important means of mass transfer in the process engineering industry. The use of supercritical fluids in industrial processes, such as extraction and particle handling, has become a more and more popular method. Take a closer look at the two processes one would find that there are obviously two sub-processes involved in each of the process, namely the diffusion/nucleation as well as a phase transition procedure. Because of the operational limitations in the practice, this phase transition can-not be neglected. So it is also included in the theoretical approach. Classically to deduce conclusions from experiment results, mathematical/physical models outlining property changes and summarizing characteristics of the two processes are expected. In order to become an insight of these phenomena from the origin, and also to serve as a fundamental attribute for the numerical simulation later, the theories of statistical thermodynamics are adopted here as a proper means to describe the behaviors of the two processes. As the diffusion coefficients of the samples in our case are only of an order of approx. 10-8m2s-1, it can be assumed that the processes are in equilibrium (local changes are neglectably small), a model can be built on a general macroscopic approach for equilibrium systems, namely the Boltzmann-Gibbs distri-bution. And some rather general methods e.g. linear response theory can be applied. But as the transfer phenomena are genuinely not equilibrium systems, from this aspect a model can also be built based on the microscopic description -the kinetic theory of the behaviors of the particles of this non-equilibrium system. The characteristics under compensated gravity are also to be considered in the models. The differences and constraints between the models are to be compared and discussed. As the thermodynamic properties of a fluid are strongly dependent on the dimensions and the conditions in which the process is taken place, the models are limited to the hardware designed for this experiment setup. In order to evolve other applications, they need to be generalized and adjusted to fit the situations accordingly. As usual, the experiment data are to be submitted to these calculations to complete the models, and also to test and to proof if they satisfy some general properties of the systems that are already known. This leads to another very important part of the work -the experiments. Because of the sophistication of the behavior of fluids around their critical points, throughout the literature the theoretical description of the phase transition as well as other processes taken place under this circumstance, still depends largely on the empirical analysis. No matter how well considered a model can be, it represents only a partial and a simplified picture of the whole process. So the experimental part is of great importance not only as a support to the theoretical solution, but also as a means to get first hand data especially for the processes under investigation in this work. As solvent supercritical carbon dioxide was chosen considering its unique economical and ecological effects. As solutes DL-α-tocopherol and n-hexane were cho-sen. Two fundamental mass transfer processes are observed, namely diffusion and nucleation, both in laboratory as well as under compensated gravity (The experiment are to be performed in parabolic flight this March 2010). Both phenomena are obtained under isothermal condition through adjustments of the pressure inside a high pressure container. The container was spe-cially designed for this case. It has a cylindrical geometry with two pistons as movable walls on both sides to control the solvent volume. For diffusion a droplet of sample is fixed between two wetting barriers in the middle of the container with filled solvent -sub-critical CO2. The ex-periment pressure is reached by reducing the volume of the container above the critical pressure of the solvent. For nucleation the container is firstly filled with saturated mixture of solvent -supercritical CO2 and the sample, the experiment pressure is achieved by enlarging the volume of the container below the critical pressure of the solvent. During the experiments the pressure and temperature data are monitored and recorded. As a direct observation means a high speed camera is used, the visual changes inside are recorded through the windows integrated on the container. The experiments are carried out under three different initial conditions, namely with three start temperatures (313K, 333K and 353K), to cover the area from vicinity of the critical point. This research serves as a pilot project topic in cooperation with DLR, which has the ultimate aim of performing the experiments of mass transfer processes in a longtime microgravity facility (e.g. ISS) in order to further explore the influences and utilities of earth gravity on these basic transport processes.

Polyimide Aerogels with Three-Dimensional Cross-Linked Structure

NASA Technical Reports Server (NTRS)

Meador, Mary Ann B. (Inventor)

2016-01-01

A method for creating a three dimensional cross-linked polyimide structure includes dissolving a diamine, a dianhydride, and a triamine in a solvent, imidizing a polyamic acid gel by heating the gel, extracting the gel in a second solvent, supercritically drying the gel, and removing the solvent to create a polyimide aerogel.

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.

Colloidal infrared reflective and transparent conductive aluminum-doped zinc oxide nanocrystals

DOEpatents

Buonsanti, Raffaella; Milliron, Delia J

2015-02-24

The present invention provides a method of preparing aluminum-doped zinc oxide (AZO) nanocrystals. In an exemplary embodiment, the method includes (1) injecting a precursor mixture of a zinc precursor, an aluminum precursor, an amine, and a fatty acid in a solution of a vicinal diol in a non-coordinating solvent, thereby resulting in a reaction mixture, (2) precipitating the nanocrystals from the reaction mixture, thereby resulting in a final precipitate, and (3) dissolving the final precipitate in an apolar solvent. The present invention also provides a dispersion. In an exemplary embodiment, the dispersion includes (1) nanocrystals that are well separated from each other, where the nanocrystals are coated with surfactants and (2) an apolar solvent where the nanocrystals are suspended in the apolar solvent. The present invention also provides a film. In an exemplary embodiment, the film includes (1) a substrate and (2) nanocrystals that are evenly distributed on the substrate.

Method of performing sugar dehydration and catalyst treatment

DOEpatents

Hu, Jianli [Kennewick, WA; Holladay, Johnathan E [Kennewick, WA; Zhang, Xinjie [Burlington, MA; Wang, Yong [Richland, WA

2010-06-01

The invention includes a method of treating a solid acid catalyst. After exposing the catalyst to a mixture containing a sugar alcohol, the catalyst is washed with an organic solvent and is then exposed to a second reaction mixture. The invention includes a process for production of anhydrosugar alcohol. A solid acid catalyst is provided to convert sugar alcohol in a first sample to an anhydrosugar alcohol. The catalyst is then washed with an organic solvent and is subsequently utilized to expose a second sample. The invention includes a method for selective production of an anhydrosugar. A solid acid catalyst is provided within a reactor and anhydrosugar alcohol is formed by flowing a starting sugar alcohol into the reactor. The acid catalyst is then exposed to an organic solvent which allows a greater amount of additional anhydrosugar to be produced than would occur without exposing the acid catalyst to the organic solvent.

Exact solutions of a two parameter flux model and cryobiological applications.

PubMed

Benson, James D; Chicone, Carmen C; Critser, John K

2005-06-01

Solute-solvent transmembrane flux models are used throughout biological sciences with applications in plant biology, cryobiology (transplantation and transfusion medicine), as well as circulatory and kidney physiology. Using a standard two parameter differential equation model of solute and solvent transmembrane flux described by Jacobs [The simultaneous measurement of cell permeability to water and to dissolved substances, J. Cell. Comp. Physiol. 2 (1932) 427-444], we determine the functions that describe the intracellular water volume and moles of intracellular solute for every time t and every set of initial conditions. Here, we provide several novel biophysical applications of this theory to important biological problems. These include using this result to calculate the value of cell volume excursion maxima and minima along with the time at which they occur, a novel result that is of significant relevance to the addition and removal of permeating solutes during cryopreservation. We also present a methodology that produces extremely accurate sum of squares estimates when fitting data for cellular permeability parameter values. Finally, we show that this theory allows a significant increase in both accuracy and speed of finite element methods for multicellular volume simulations, which has critical clinical biophysical applications in cryosurgical approaches to cancer treatment.

Deashing of coal liquids with ceramic membrane microfiltration and diafiltration

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

Bishop, B.; Goldsmith, R.

1995-12-31

Removal of mineral matter from liquid hydrocarbons derived from the direct liquefaction of coal is required for product acceptability. Current methods include critical solvent deashing (Rose{sup {reg_sign}} process from Kerr-McGee) and filtration (U.S. Filter leaf filter as used by British Coal). These methods produce ash reject streams containing up to 15% of the liquid hydrocarbon product. Consequently, CeraMem proposed the use of low cost, ceramic crossflow membranes for the filtration of coal liquids bottoms to remove mineral matter and subsequent diafiltration (analogous to cake washing in dead-ended filtration) for the removal of coal liquid from the solids stream. The usemore » of these ceramic crossflow membranes overcomes the limitations of traditional polymeric crossflow membranes by having the ability to operate at elevated temperature and to withstand prolonged exposure to hydrocarbon and solvent media. In addition, CeraMem`s membrane filters are significantly less expensive than competitive ceramic membranes due to their unique construction. With these ceramic membrane filters, it may be possible to reduce the product losses associated with traditional deashing processes at an economically attractive cost. The performance of these ceramic membrane microfilters is discussed.« less

Halogenated solvent remediation

DOEpatents

Sorenson, Jr., Kent S.

2008-11-11

Methods for enhancing bioremediation of ground water contaminated with nonaqueous halogenated solvents are disclosed. An illustrative method includes adding an electron donor for microbe-mediated anaerobic reductive dehalogenation of the halogenated solvents, which electron donor enhances mass transfer of the halogenated solvents from residual source areas into the aqueous phase of the ground water. Illustrative electron donors include C.sub.2-C.sub.4 carboxylic acids and hydroxy acids, salts thereof, esters of C.sub.2-C.sub.4 carboxylic acids and hydroxy acids, and mixtures thereof, of which lactic acid, salts of lactic acid--such as sodium lactate, lactate esters, and mixtures thereof are particularly illustrative. The microbes are either indigenous to the ground water, or such microbes can be added to the ground water in addition to the electron donor.

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

NASA Technical Reports Server (NTRS)

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

2012-01-01

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

Driven polymer translocation in good and bad solvent: Effects of hydrodynamics and tension propagation.

PubMed

Moisio, J E; Piili, J; Linna, R P

2016-08-01

We investigate the driven polymer translocation through a nanometer-scale pore in the presence and absence of hydrodynamics both in good and bad solvent. We present our results on tension propagating along the polymer segment on the cis side that is measured for the first time using our method that works also in the presence of hydrodynamics. For simulations we use stochastic rotation dynamics, also called multiparticle collision dynamics. We find that in the good solvent the tension propagates very similarly whether hydrodynamics is included or not. Only the tensed segment is by a constant factor shorter in the presence of hydrodynamics. The shorter tensed segment and the hydrodynamic interactions contribute to a smaller friction for the translocating polymer when hydrodynamics is included, which shows as smaller waiting times and a smaller exponent in the scaling of the translocation time with the polymer length. In the bad solvent hydrodynamics has a minimal effect on polymer translocation, in contrast to the good solvent, where it speeds up translocation. We find that under bad-solvent conditions tension does not spread appreciably along the polymer. Consequently, translocation time does not scale with the polymer length. By measuring the effective friction in a setup where a polymer in free solvent is pulled by a constant force at the end, we find that hydrodynamics does speed up collective polymer motion in the bad solvent even more effectively than in the good solvent. However, hydrodynamics has a negligible effect on the motion of individual monomers within the highly correlated globular conformation on the cis side and hence on the entire driven translocation under bad-solvent conditions.

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

PubMed Central

Baker, Nathan A.; McCammon, J. Andrew

2008-01-01

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

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

NASA Astrophysics Data System (ADS)

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

2007-10-01

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

Organic solvent regeneration of granular activated carbon

NASA Astrophysics Data System (ADS)

Cross, W. H.; Suidan, M. T.; Roller, M. A.; Kim, B. R.; Gould, J. P.

1982-09-01

The use of activated carbon for the treatment of industrial waste-streams was shown to be an effective treatment. The high costs associated with the replacement or thermal regeneration of the carbon have prohibited the economic feasibility of this process. The in situ solvent regeneration of activated carbon by means of organic solvent extraction was suggested as an economically alternative to thermal regeneration. The important aspects of the solvent regeneration process include: the physical and chemical characteristics of the adsorbent, the pore size distribution and energy of adsorption associated with the activated carbon; the degree of solubility of the adsorbate in the organic solvent; the miscibility of the organic solvent in water; and the temperature at which the generation is performed.

Self-Assembly, Surface Activity and Structure of n-Octyl-β-D-thioglucopyranoside in Ethylene Glycol-Water Mixtures

PubMed Central

Ruiz, Cristóbal Carnero; Molina-Bolívar, José Antonio; Hierrezuelo, José Manuel; Liger, Esperanza

2013-01-01

The effect of the addition of ethylene glycol (EG) on the interfacial adsorption and micellar properties of the alkylglucoside surfactant n-octyl-β-d-thioglucopyranoside (OTG) has been investigated. Critical micelle concentrations (cmc) upon EG addition were obtained by both surface tension measurements and the pyrene 1:3 ratio method. A systematic increase in the cmc induced by the presence of the co-solvent was observed. This behavior was attributed to a reduction in the cohesive energy of the mixed solvent with respect to pure water, which favors an increase in the solubility of the surfactant with EG content. Static light scattering measurements revealed a decrease in the mean aggregation number of the OTG micelles with EG addition. Moreover, dynamic light scattering data showed that the effect of the surfactant concentration on micellar size is also controlled by the content of the co-solvent in the system. Finally, the effect of EG addition on the microstructure of OTG micelles was investigated using the hydrophobic probe Coumarin 153 (C153). Time-resolved fluorescence anisotropy decay curves of the probe solubilized in micelles were analyzed using the two-step model. The results indicate a slight reduction of the average reorientation time of the probe molecule with increasing EG in the mixed solvent system, thereby suggesting a lesser compactness induced by the presence of the co-solvent. PMID:23385232

Self-assembly, surface activity and structure of n-octyl-β-D-thioglucopyranoside in ethylene glycol-water mixtures.

PubMed

Ruiz, Cristóbal Carnero; Molina-Bolívar, José Antonio; Hierrezuelo, José Manuel; Liger, Esperanza

2013-02-05

The effect of the addition of ethylene glycol (EG) on the interfacial adsorption and micellar properties of the alkylglucoside surfactant n-octyl-β-D-thioglucopyranoside (OTG) has been investigated. Critical micelle concentrations (cmc) upon EG addition were obtained by both surface tension measurements and the pyrene 1:3 ratio method. A systematic increase in the cmc induced by the presence of the co-solvent was observed. This behavior was attributed to a reduction in the cohesive energy of the mixed solvent with respect to pure water, which favors an increase in the solubility of the surfactant with EG content. Static light scattering measurements revealed a decrease in the mean aggregation number of the OTG micelles with EG addition. Moreover, dynamic light scattering data showed that the effect of the surfactant concentration on micellar size is also controlled by the content of the co-solvent in the system. Finally, the effect of EG addition on the microstructure of OTG micelles was investigated using the hydrophobic probe Coumarin 153 (C153). Time-resolved fluorescence anisotropy decay curves of the probe solubilized in micelles were analyzed using the two-step model. The results indicate a slight reduction of the average reorientation time of the probe molecule with increasing EG in the mixed solvent system, thereby suggesting a lesser compactness induced by the presence of the co-solvent.

Stretch-collapse transition of polyelectrolyte brushes in a poor solvent

NASA Astrophysics Data System (ADS)

von Goeler, F.; Muthukumar, M.

1996-12-01

This paper describes the behavior of charged, polymer brushes in electrolyte solutions of varying solvent quality. The brush height, d, dependence on the chain length, L (=Nl, where l is the Kuhn length), the grafting density σ, and solvent conditions is determined. We consider a monomer-monomer potential consisting of three components: (1) a long-ranged, screened Coulombic component of strength v¯/l (l is the Kuhn length) and range κ-1; (2) a short-ranged, two-body component of strength w¯l; and (3) a short-ranged, three-body component of strength ūl3. In particular, we examine the transition from a stretched state to a collapsed state in a poor solvent (w¯<0) as the solvent quality is decreased. Using dimensional analysis, Monte Carlo methods, and a variational technique, a first order transition is observed as predicted by the scaling arguments of Ross et al. and Borisov et al. for high charge/grafting densities. Using a variational procedure, we derive an analytical expression for the brush size and determine, quantitatively, the critical conditions for a first order transition in terms of key dimensionless variables, vN5/2, κlN1/2, wN3/2, and uN2 (where v=2πσl2v¯, w=σl2w¯, and u=σ2l4ū).

Inert Reassessment Document for n-Butanol

EPA Pesticide Factsheets

The butyl alcohols are widely-used industrial solvents. Applications include solvents for paints, lacquers, varnishes, natural and synthetic resins, gums,vegetable oils, dyes, camphor, alkaloids, and pesticides.

Method for removing contaminants from plastic resin

DOEpatents

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

2008-12-09

A resin recycling method that produces essentially contaminant-free synthetic resin material in an environmentally safe and economical manner. The method includes receiving the resin in container form. The containers are then ground into resin particles. The particles are exposed to a solvent, the solvent contacting the resin particles and substantially removing contaminants on the resin particles. After separating the particles and the resin, a solvent removing agent is used to remove any residual solvent remaining on the resin particles after separation.

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

NASA Technical Reports Server (NTRS)

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

2016-01-01

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

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

Investigation of solvent-free MALDI-TOFMS sample preparation methods for the analysis of organometallic and coordination compounds.

PubMed

Hughes, Laura; Wyatt, Mark F; Stein, Bridget K; Brenton, A Gareth

2009-01-15

An investigation of various solvent-free matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS) sample preparation methods for the characterization of organometallic and coordination compounds is described. Such methods are desirable for insoluble materials, compounds that are only soluble in disadvantageous solvents, or complexes that dissociate in solution, all of which present a major "difficulty" to most mass spectrometry techniques. First-row transition metal acetylacetonate complexes, which have been characterized previously by solution preparation MALDI-TOFMS, were used to evaluate the various solvent-free procedures. These procedures comprise two distinct steps: the first being the efficient "solids mixing" (the mixing of sample and matrix), and the second being the effective transfer of the sample/matrix mixture to the MALDI target plate. This investigation shows that vortex mixing is the most efficient first step and that smearing using a microspatula is the most effective second step. In addition, the second step is shown to be much more critical than the first step in obtaining high-quality data. Case studies of truly insoluble materials highlight the importance of these techniques for the wider chemistry community.

Operation of the solvent-refined-coal pilot plant, Wilsonville, Alabama. Annual technical report, January-December 1980

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

Lewis, H.E.

1981-08-01

The plant was in operation for the equivalent of 247 days, an on-stream factor of 67.7%. Kentucky 9 coals from the Lafayette, Dotiki and Fies mines were processed. During 1980, the operating conditions and equipment were adjusted to evaluate potential process improvements. These experiments produced significant results in the following areas: Operating V103 High Pressure Separator in the hot mode; varying T102 Vacuum Column operating temperature; adding light SRC (LSRC), a product of the third stage of the Critical Solvent Deashing (CSD) unit, to the process solvent; investigating the effects of the chlorine content of the feed coal on corrosionmore » in the process vessels; evaluating the effects of adding sodium carbonate on corrosion rates; operating under conditions of low severity; i.e., low reactor temperature and long residence time; and testing an alternate CSD deashing solvent. A series of simulation runs investigating the design operating conditions for a planned 6000 ton per day SRC-I demonstation plant were also completed. Numerous improvements were made in the CSD processing area, and the components for a hydrotreating unit were installed.« less

40 CFR 60.601 - Definitions.

Code of Federal Regulations, 2014 CFR

2014-07-01

... means the water, solvent, or other chemical bath into which the polymer or prepolymer (partially reacted..., transportation, collection, concentration, and purification of organic solvents. It may include enclosures, hoods...

40 CFR 60.601 - Definitions.

Code of Federal Regulations, 2010 CFR

2010-07-01

... means the water, solvent, or other chemical bath into which the polymer or prepolymer (partially reacted..., transportation, collection, concentration, and purification of organic solvents. It may include enclosures, hoods...

40 CFR 60.601 - Definitions.

Code of Federal Regulations, 2013 CFR

2013-07-01

... means the water, solvent, or other chemical bath into which the polymer or prepolymer (partially reacted..., transportation, collection, concentration, and purification of organic solvents. It may include enclosures, hoods...

40 CFR 60.601 - Definitions.

Code of Federal Regulations, 2012 CFR

2012-07-01

... means the water, solvent, or other chemical bath into which the polymer or prepolymer (partially reacted..., transportation, collection, concentration, and purification of organic solvents. It may include enclosures, hoods...

40 CFR 60.601 - Definitions.

Code of Federal Regulations, 2011 CFR

2011-07-01

... means the water, solvent, or other chemical bath into which the polymer or prepolymer (partially reacted..., transportation, collection, concentration, and purification of organic solvents. It may include enclosures, hoods...

Semiconductor liquid crystal composition and methods for making the same

DOEpatents

Alivisatos, A. Paul; Li, Liang-shi

2005-04-26

Semiconductor liquid crystal compositions and methods for making such compositions are disclosed. One embodiment of the invention is directed to a liquid crystal composition including a solvent and semiconductor particles in the solvent. The solvent and the semiconductor particles are in an effective amount in the liquid crystal composition to form a liquid crystal phase.

Selection of polymer binders and fabrication of SiC fiber-reinforced reaction-bonded silicon nitride matrix composites

NASA Technical Reports Server (NTRS)

Haggerty, John S.; Lightfoot, A.; Sigalovsky, J.

1993-01-01

The topics discussed include the following: effects of solvent and polymer exposures on nitriding kinetics of high purity Si powders and on resulting phase distributions; effects of solvent and polymer exposures on Si Surface Chemistry; effects of solvent and polymeric exposures on nitriding kinetics; and fabrication of flexural test samples.

Crystal growth in fused solvent systems

NASA Technical Reports Server (NTRS)

Ulrich, D. R.; Noone, M. J.; Spear, K. E.; White, W. B.; Henry, E. C.

1973-01-01

Research is reported on the growth of electronic ceramic single crystals from solution for the future growth of crystals in a microgravity environment. Work included growth from fused or glass solvents and aqueous solutions. Topics discussed include: crystal identification and selection; aqueous solution growth of triglycine sulphate (TGS); and characterization of TGS.

FINAL REPORT: Room Temperature Hydrogen Storage in Nano-Confined Liquids

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

VAJO, JOHN

2014-06-12

DOE continues to seek solid-state hydrogen storage materials with hydrogen densities of ≥6 wt% and ≥50 g/L that can deliver hydrogen and be recharged at room temperature and moderate pressures enabling widespread use in transportation applications. Meanwhile, development including vehicle engineering and delivery infrastructure continues for compressed-gas hydrogen storage systems. Although compressed gas storage avoids the materials-based issues associated with solid-state storage, achieving acceptable volumetric densities has been a persistent challenge. This project examined the possibility of developing storage materials that would be compatible with compressed gas storage technology based on enhanced hydrogen solubility in nano-confined liquid solvents. These materialsmore » would store hydrogen in molecular form eliminating many limitations of current solid-state materials while increasing the volumetric capacity of compressed hydrogen storage vessels. Experimental methods were developed to study hydrogen solubility in nano-confined liquids. These methods included 1) fabrication of composites comprised of volatile liquid solvents for hydrogen confined within the nano-sized pore volume of nanoporous scaffolds and 2) measuring the hydrogen uptake capacity of these composites without altering the composite composition. The hydrogen storage capacities of these nano-confined solvent/scaffold composites were compared with bulk solvents and with empty scaffolds. The solvents and scaffolds were varied to optimize the enhancement in hydrogen solubility that accompanies confinement of the solvent. In addition, computational simulations were performed to study the molecular-scale structure of liquid solvent when confined within an atomically realistic nano-sized pore of a model scaffold. Confined solvent was compared with similar simulations of bulk solvent. The results from the simulations were used to formulate a mechanism for the enhanced solubility and to guide the experiments. Overall, the combined experimental measurements and simulations indicate that hydrogen storage based on enhanced solubility in nano-confined liquids is unlikely to meet the storage densities required for practical use. Only low gravimetric capacities of < 0.5 wt% were achieved. More importantly, solvent filled scaffolds had lower volumetric capacities than corresponding empty scaffolds. Nevertheless, several of the composites measured did show significant (>~ 5x) enhanced hydrogen solubility relative to bulk solvent solubility, when the hydrogen capacity was attributed only to dissolution in the confined solvent. However, when the hydrogen capacity was compared to an empty scaffold that is known to store hydrogen by surface adsorption on the scaffold walls, including the solvent always reduced the hydrogen capacity. For the best composites, this reduction relative to an empty scaffold was ~30%; for the worst it was ~90%. The highest capacities were obtained with the largest solvent molecules and with scaffolds containing 3- dimensionally confined pore geometries. The simulations suggested that the capacity of the composites originated from hydrogen adsorption on the scaffold pore walls at sites not occupied by solvent molecules. Although liquid solvent filled the pores, not all of the adsorption sites on the pore walls were occupied due to restricted motion of the solvent molecules within the confined pore space.« less

Sub-slab vs. Near-slab Soil Vapor Profiles at a Chlorinated Solvent Site (1)

EPA Science Inventory

A critical issue in assessing the vapor intrusion pathway is the distribution and migration of VOCs from the subsurface source to the near surface environment. Of particular importance is the influence of a slab. Therefore, EPA/ORD is funding a research program with the primary...

Sub-slab vs. Near-slab Soil Vapor Profiles at a Chlorinated Solvent Site

EPA Science Inventory

A critical issue in assessing the vapor intrusion pathway is the distribution and migration of VOCs from the subsurface source to the near surface environment. Therefore, EPA/ORD funded a research project with the primary goal of comparing vertical profiles of soil gas concentrat...

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

Guo, Wei; Reese, Cassandra M.; Xiong, Li

We report a simple route to engineer ultrathin polymer brush surfaces with wrinkled morphologies using postpolymerization modification (PPM), where the length scale of the buckled features can be tuned using PPM reaction time. Here, we show that partial crosslinking of the outer layer of the polymer brush under poor solvent conditions is critical to obtain wrinkled morphologies upon swelling.

MODELING THE TOXICOKINETICS OF INHALED TOLUENE IN RATS: THE IMPACT OF CONDITIONING AND PHYSICAL ACTIVITY

EPA Science Inventory

Toluene is found in petroleum-based fuels and used as a solvent in consumer products and industrial applications. The critical effects following inhalation exposure involve the brain and nervous system in both humans and experimental animals whether exposure duration is acute or...

MODELING THE TOXICOKINETICS OF INHALED TOLUENE IN RATS: THE IMPACT OF FEEDING STATUS, PHYSICAL ACTIVITY AND STRAIN

EPA Science Inventory

Toluene is found in petroleum-based fuels and used as a solvent in consumer products and industrial applications. The critical effects following inhalation exposure involve the brain and nervous system in both humans and experimental animals whether exposure duration is acute or...

Oligomerization of jojoba oil in super-critical carbon dioxide (green solvent) for different applications

USDA-ARS?s Scientific Manuscript database

Vegetable oils are renewable, non-toxic, biodegradable, non-polluting, and relatively harmless to the environment. Approximately 80% of the global plant oil and fat production is from vegetable oil, whereas 20% is from animal origin (share decreasing). Jojoba (Simmondsia chinensis) is a perennial sh...

Modeling the toxicokinetics of 24-hour toluene exposure in rats, impact of activity patterns and enzyme induction

EPA Science Inventory

Toluene, a solvent used in numerous consumer and industrial applications, exerts its critical effects on the brain and nervous system following inhalation exposure. Our previously published PBPK model successfully predicted toluene concentrations in blood and brain over a range o...

Oil shale extraction using super-critical extraction

NASA Technical Reports Server (NTRS)

Compton, L. E. (Inventor)

1983-01-01

Significant improvement in oil shale extraction under supercritical conditions is provided by extracting the shale at a temperature below 400 C, such as from about 250 C to about 350 C, with a solvent having a Hildebrand solubility parameter within 1 to 2 Hb of the solubility parameter for oil shale bitumen.

Chrysin cocrystals: Characterization and evaluation.

PubMed

Chadha, Renu; Bhalla, Yashika; Nandan, Avdesh; Chadha, Kunal; Karan, Maninder

2017-02-05

Solvent free mechanochemical approach is utilized to synthesise new cocrystals of chrysin using supramolecular chemistry based upon reliable synthons. Chrysin, a flavone nutraceutical with wide range of beneficial effects has critically low bioavailability on account of its poor aqueous solubility and consequently poor absorption from the gastrointestinal tract. The present study focuses on this critical aspect and has exploited non covalent interactions to prepare its cocrystals with cytosine and thiamine hydrochloride. Various techniques were used for characterization including Differential Scanning Calorimetry (DSC), Fourier Transform Infrared Spectroscopy (FT-IR), Solid State NMR Spectroscopy (SSNMR) and Powder X-Ray Diffraction (PXRD). The molecules in the cocrystals crystallized in neutral forms and assembled in a molecular layer by means of hydrogen bonding which was confirmed by structural characterization. The cocrystals share a common supramolecular motif being the OH⋯N arom interaction, involving phenolic moiety of C7 functionality of the parent molecule. Approximately 3-4 fold increase in solubility and dissolution profile of cocrystals was observed which was further corroborated by improved in vitro and in vivo activities including antioxidant, antihaemolytic and anti-inflammatory thus, opening a new viable technique for the exploitation of useful phytonutrients. Copyright © 2016 Elsevier B.V. All rights reserved.

Thermodynamic description of cellulose chain collapse using coarse grain modeling

NASA Astrophysics Data System (ADS)

Das, Ritankar; Chu, Jhih-Wei

2012-11-01

Biomass contains abundant amounts of cellulose as crystalline microfibrils. A limiting step to using cellulose as an alternative energy source, however, is the hydrolysis of the biomass and subsequent transformation into fuels. Cellulose is insoluble in most solvents including organic solvents and water, but it is soluble in some ionic liquids like BMIM-Cl. This project aims to find alternative solvents that are less expensive and are more environmentally benign than the ionic liquids. All-atom molecular dynamics simulations were performed on dissociated glucan chains separated by multiple (4-5) solvation shells, in the presence of several novel solvents and solvent mixtures. The solubility of the chains in each solvent was indicated by contacts calculations after the equilibration of the molecular dynamics. It was discovered that pyridine and imidazole acted as the best solvents because their aromatic electronic structure was able to effectively disrupt the inter-sheet interactions among the glucan chains in the axial direction, and because perturbation of the solvent interactions in the presence of glucan chains was minimal.

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

NASA Astrophysics Data System (ADS)

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

2016-12-01

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

Microbial process for the preparation of acetic acid as well as solvent for its extraction from the fermentation broth

DOEpatents

Gaddy, James L.; Clausen, Edgar C.; Ko, Ching-Whan; Wade, Leslie E.; Wikstrom, Carl V.

2006-07-11

A modified water-immiscible solvent useful in the extraction of acetic acid from aqueous streams is a substantially pure mixture of isomers of highly branched di-alkyl amines. This solvent is substantially devoid of mono-alkyl amines and alcohols. Solvent mixtures formed of such a modified solvent with a desired cosolvent, preferably a low boiling hydrocarbon which forms an azeotrope with water are useful in the extraction of acetic acid from aqueous gaseous streams. An anaerobic microbial fermentation process for the production of acetic acid employs such solvents, under conditions which limit amide formation by the solvent and thus increase the efficiency of acetic acid recovery. Methods for the direct extraction of acetic acid and the extractive fermentation of acetic acid also employ the modified solvents and increase efficiency of acetic acid production. Such increases in efficiency are also obtained where the energy source for the microbial fermentation contains carbon dioxide and the method includes a carbon dioxide stripping step prior to extraction of acetic acid in solvent.

Microbial process for the preparation of acetic acid as well as solvent for its extraction from the fermentation broth

DOEpatents

Gaddy, James L.; Clausen, Edgar C.; Ko, Ching-Whan; Wade, Leslie E.; Wikstrom, Carl V.

2002-01-01

A modified water-immiscible solvent useful in the extraction of acetic acid from aqueous streams is a substantially pure mixture of isomers of highly branched di-alkyl amines. This solvent is substantially devoid of mono-alkyl amines and alcohols. Solvent mixtures formed of such a modified solvent with a desired cosolvent, preferably a low boiling hydrocarbon which forms an azeotrope with water are useful in the extraction of acetic acid from aqueous gaseous streams. An anaerobic microbial fermentation process for the production of acetic acid employs such solvents, under conditions which limit amide formation by the solvent and thus increase the efficiency of acetic acid recovery. Methods for the direct extraction of acetic acid and the extractive fermentation of acetic acid also employ the modified solvents and increase efficiency of acetic acid production. Such increases in efficiency are also obtained where the energy source for the microbial fermentation contains carbon dioxide and the method includes a carbon dioxide stripping step prior to extraction of acetic acid in solvent.

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.

Morphological Evolution of Block Copolymer Particles: Effect of Solvent Evaporation Rate on Particle Shape and Morphology.

PubMed

Shin, Jae Man; Kim, YongJoo; Yun, Hongseok; Yi, Gi-Ra; Kim, Bumjoon J

2017-02-28

Shape and morphology of polymeric particles are of great importance in controlling their optical properties or self-assembly into unusual superstructures. Confinement of block copolymers (BCPs) in evaporative emulsions affords particles with diverse structures, including prolate ellipsoids, onion-like spheres, oblate ellipsoids, and others. Herein, we report that the evaporation rate of solvent from emulsions encapsulating symmetric polystyrene-b-polybutadiene (PS-b-PB) determines the shape and internal nanostructure of micron-sized BCP particles. A distinct morphological transition from the ellipsoids with striped lamellae to the onion-like spheres was observed with decreasing evaporation rate. Experiments and dissipative particle dynamics (DPD) simulations showed that the evaporation rate affected the organization of BCPs at the particle surface, which determined the final shape and internal nanostructure of the particles. Differences in the solvent diffusion rates in PS and PB at rapid evaporation rates induced alignment of both domains perpendicular to the particle surface, resulting in ellipsoids with axial lamellar stripes. Slower evaporation rates provided sufficient time for BCP organization into onion-like structures with PB as the outermost layer, owing to the preferential interaction of PB with the surroundings. BCP molecular weight was found to influence the critical evaporation rate corresponding to the morphological transition from ellipsoid to onion-like particles, as well as the ellipsoid aspect ratio. DPD simulations produced morphologies similar to those obtained from experiments and thus elucidated the mechanism and driving forces responsible for the evaporation-induced assembly of BCPs into particles with well-defined shapes and morphologies.

Multiple source/multiple target fluid transfer apparatus

DOEpatents

Turner, Terry D.

1997-01-01

A fluid transfer apparatus includes: a) a plurality of orifices for connection with fluid sources; b) a plurality of orifices for connection with fluid targets; c) a set of fluid source conduits and fluid target conduits associated with the orifices; d) a pump fluidically interposed between the source and target conduits to transfer fluid therebetween; e) a purge gas conduit in fluid communication with the fluid source conduits, fluid target conduits and pump to receive and pass a purge gas under pressure; f) a solvent conduit in fluid communication with the fluid source conduits, fluid target conduits and pump to receive and pass solvent, the solvent conduit including a solvent valve; g) pump control means for controlling operation of the pump; h) purge gas valve control means for controlling operation of the purge gas valve to selectively impart flow of purge gas to the fluid source conduits, fluid target conduits and pump; i) solvent valve control means for controlling operation of the solvent valve to selectively impart flow of solvent to the fluid source conduits, fluid target conduits and pump; and j) source and target valve control means for controlling operation of the fluid source conduit valves and the fluid target conduit valves to selectively impart passage of fluid between a selected one of the fluid source conduits and a selected one of the fluid target conduits through the pump and to enable passage of solvent or purge gas through selected fluid source conduits and selected fluid target conduits.

Multiple source/multiple target fluid transfer apparatus

DOEpatents

Turner, T.D.

1997-08-26

A fluid transfer apparatus includes: (a) a plurality of orifices for connection with fluid sources; (b) a plurality of orifices for connection with fluid targets; (c) a set of fluid source conduits and fluid target conduits associated with the orifices; (d) a pump fluidically interposed between the source and target conduits to transfer fluid there between; (e) a purge gas conduit in fluid communication with the fluid source conduits, fluid target conduits and pump to receive and pass a purge gas under pressure; (f) a solvent conduit in fluid communication with the fluid source conduits, fluid target conduits and pump to receive and pass solvent, the solvent conduit including a solvent valve; (g) pump control means for controlling operation of the pump; (h) purge gas valve control means for controlling operation of the purge gas valve to selectively impart flow of purge gas to the fluid source conduits, fluid target conduits and pump; (i) solvent valve control means for controlling operation of the solvent valve to selectively impart flow of solvent to the fluid source conduits, fluid target conduits and pump; and (j) source and target valve control means for controlling operation of the fluid source conduit valves and the fluid target conduit valves to selectively impart passage of fluid between a selected one of the fluid source conduits and a selected one of the fluid target conduits through the pump and to enable passage of solvent or purge gas through selected fluid source conduits and selected fluid target conduits. 6 figs.

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

NASA Technical Reports Server (NTRS)

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

2002-01-01

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

Computer-aided solvent selection for multiple scenarios operation of limited-known properties solute

NASA Astrophysics Data System (ADS)

Anantpinijwatna, Amata

2017-12-01

Solvents have been applied for both production and separation of the complex chemical substance such as the pyrrolidine-2-carbonyl chloride (C5H8ClNO). Since the properties of the target substance itself are largely unknown, the selection of the solvent is limited by experiment only. However, the reaction carried out in conventional solvents are either afforded low yields or obtained slow reaction rates. Moreover, the solvents are also highly toxic and environmental unfriendly. Alternative solvents are required to enhance the production and lessen the harmful effect toward both organism and environment. A costly, time-consuming, and laborious experiments are required for acquiring a better solvent suite for production and separation of these complex compounds; whereas, a limited improvement can be obtained. On the other hand, the combination of the state-of-the-art thermodynamic models can provide faster and more robust solutions to this solvent selection problem. In this work, a framework for solvents selection in complex chemical production process is presented. The framework combines a group-contribution thermodynamic model and a segment activity coefficient model for predicting chemical properties and solubilities of the target chemical in newly formulated solvents. A guideline for solvent selection is also included. The potential of the selected solvents is then analysed and verified. The improvement toward the production yield, production rate, and product separation is then discussed.

Portable Spray Booth

NASA Technical Reports Server (NTRS)

Hansen, Timothy D.; Bardwell, Micheal J.

1996-01-01

Portable spray booth provides for controlled application of coating materials with high solvent contents. Includes contoured shroud and carbon filter bed limiting concentration of fumes in vicinity. Designed to substitute spraying for brush application of solvent-based adhesive prior to installing rubber waterproof seals over joints between segments of solid-fuel rocket motor. With minor adjustments and modifications, used to apply other solvent-based adhesives, paints, and like.

Impaired colour vision in workers exposed to organic solvents: A systematic review.

PubMed

Betancur-Sánchez, A M; Vásquez-Trespalacios, E M; Sardi-Correa, C

2017-01-01

To evaluate recent evidence concerning the relationship between the exposure to organic solvents and the impairment of colour vision. A bibliographic search was conducted for scientific papers published in the last 15 years, in the LILACS, PubMed, Science Direct, EBSCO, and Cochrane databases that included observational studies assessing the relationship between impairment in colour vision and exposure to organic solvents. Eleven studies were selected that were performed on an economically active population and used the Lanthony D-15 desaturated test (D-15d), measured the exposure to organic solvents, and included unexposed controls. It was found that there is a statistically significant relationship between the exposure to organic solvents and the presence of an impairment in colour vision. The results support the hypothesis that exposure to organic solvents could induce acquired dyschromatopsia. The evaluation of colour vision with the D-15d test is simple and sensitive for diagnosis. More studies need to be conducted on this subject in order to better understand the relationship between impaired colour vision and more severe side effects caused by this exposure. Copyright © 2016 Sociedad Española de Oftalmología. Publicado por Elsevier España, S.L.U. All rights reserved.

Combinations of fluorinated solvents with imide salts or methide salts for electrolytes

DOEpatents

Tikhonov, Konstantin; Yip, Ka Ki; Lin, Tzu-Yuan; Lei, Norman; Guerrero-Zavala, Guillermo; Kwong, Kristie W

2015-11-10

Provided are electrochemical cells and electrolytes used to build such cells. The electrolytes include imide salts and/or methide salts as well as fluorinated solvents capable of maintaining single phase solutions at between about -30.degree. C. to about 80.degree. C. The fluorinated solvents, such as fluorinated carbonates, fluorinated esters, and fluorinated esters, are less flammable than their non-fluorinated counterparts and improve safety characteristics of cells containing these solvents. The amount of fluorinated solvents in electrolytes may be between about 30% and 80% by weight not accounting weight of the salts. Linear and cyclic imide salts, such as LiN(SO.sub.2CF.sub.2CF.sub.3).sub.2, and LiN(SO.sub.2CF.sub.3).sub.2, as well as methide salts, such as LiC(SO.sub.2CF.sub.3).sub.3 and LiC(SO.sub.2CF.sub.2CF.sub.3).sub.3, may be used in these electrolytes. Fluorinated alkyl groups enhance solubility of these salts in the fluorinated solvents. In some embodiments, the electrolyte may also include a flame retardant, such as a phosphazene, and/or one or more ionic liquids.

First-principles study of solvent-solute mixed dumbbells in body-centered-cubic tungsten crystals

NASA Astrophysics Data System (ADS)

Suzudo, Tomoaki; Tsuru, Tomohito; Hasegawa, Akira

2018-07-01

Tungsten (W) is considered as a promising candidate for plasma-facing materials for future nuclear fusion devices, and selecting optimal alloying constituents is a critical issue to improve radiation resistance of the W alloys as well as to improve their mechanical properties. We conducted in the current study a series of first-principles calculations for investigating solvent-solute mixed dumbbells in W crystals. The results suggested that titanium (Ti), vanadium (V), and chromium (Cr) are favorable as solutes for W alloys from irradiation-effect perspectives because these elements are expected to promote vacancy-interstitial recombination without causing radiation-induced precipitation that reduces ductility of irradiated materials.

Analytical phase diagrams for colloids and non-adsorbing polymer.

PubMed

Fleer, Gerard J; Tuinier, Remco

2008-11-04

We review the free-volume theory (FVT) of Lekkerkerker et al. [Europhys. Lett. 20 (1992) 559] for the phase behavior of colloids in the presence of non-adsorbing polymer and we extend this theory in several aspects: (i) We take the solvent into account as a separate component and show that the natural thermodynamic parameter for the polymer properties is the insertion work Pi(v), where Pi is the osmotic pressure of the (external) polymer solution and v the volume of a colloid particle. (ii) Curvature effects are included along the lines of Aarts et al. [J. Phys.: Condens. Matt. 14 (2002) 7551] but we find accurate simple power laws which simplify the mathematical procedure considerably. (iii) We find analytical forms for the first, second, and third derivatives of the grand potential, needed for the calculation of the colloid chemical potential, the pressure, gas-liquid critical points and the critical endpoint (cep), where the (stable) critical line ends and then coincides with the triple point. This cep determines the boundary condition for a stable liquid. We first apply these modifications to the so-called colloid limit, where the size ratio q(R)=R/a between the radius of gyration R of the polymer and the particle radius a is small. In this limit the binodal polymer concentrations are below overlap: the depletion thickness delta is nearly equal to R, and Pi can be approximated by the ideal (van't Hoff) law Pi=Pi(0)=phi/N, where phi is the polymer volume fraction and N the number of segments per chain. The results are close to those of the original Lekkerkerker theory. However, our analysis enables very simple analytical expressions for the polymer and colloid concentrations in the critical and triple points and along the binodals as a function of q(R). Also the position of the cep is found analytically. In order to make the model applicable to higher size ratio's q(R) (including the so-called protein limit where q(R)>1) further extensions are needed. We introduce the size ratio q=delta/a, where the depletion thickness delta is no longer of order R. In the protein limit the binodal concentrations are above overlap. In such semidilute solutions delta approximately xi, where the De Gennes blob size (correlation length) xi scales as xi approximately phi(-gamma), with gamma=0.77 for good solvents and gamma=1 for a theta solvent. In this limit Pi=Pi(sd) approximately phi(3gamma). We now apply the following additional modifications: With these latter two modifications we obtain again a fully analytical model with simple equations for critical and triple points as a function of q(R). In the protein limit the binodal polymer concentrations scale as q(R)(1/gamma), and phase diagrams phiq(R)(-1/gamma) versus the colloid concentration eta become universal (i.e., independent of the size ratio q(R)). The predictions of this generalized free-volume theory (GFVT) are in excellent agreement with experiment and with computer simulations, not only for the colloid limit but also for the protein limit (and the crossover between these limits). The q(R)(1/gamma) scaling is accurately reproduced by both simulations and other theoretical models. The liquid window is the region between phi(c) (critical point) and phi(t) (triple point). In terms of the ratio phi(t)/phi(c) the liquid window extends from 1 in the cep (here phi(t)-phi(c)=0) to 2.2 in the protein limit. Hence, the liquid window is narrow: it covers at most a factor 2.2 in (external) polymer concentration.

A Nanophase-Separated, Quasi-Solid-State Polymeric Single-Ion Conductor: Polysulfide Exclusion for Lithium–Sulfur Batteries

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

Lee, Jinhong; Song, Jongchan; Lee, Hongkyung

Formation of soluble polysulfide (PS), which is a key feature of lithium sulfur (Li–S) batteries, provides a fast redox kinetic based on a liquid–solid mechanism; however, it imposes the critical problem of PS shuttle. Here, we address the dilemma by exploiting a solvent-swollen polymeric single-ion conductor (SPSIC) as the electrolyte medium of the Li–S battery. The SPSIC consisting of a polymeric single-ion conductor and lithium salt-free organic solvents provides Li ion hopping by forming a nanoscale conducting channel and suppresses PS shuttle according to the Donnan exclusion principle when being employed for Li–S batteries. The organic solvents at the interfacemore » of the sulfur/carbon composite and SPSIC eliminate the poor interfacial contact and function as a soluble PS reservoir for maintaining the liquid–solid mechanism. Furthermore, the quasi-solid-state SPSIC allows the fabrication of a bipolar-type stack, which promises the realization of a high-voltage and energy-dense Li–S battery.« less

Transport equations of electrodiffusion processes in the laboratory reference frame.

PubMed

Garrido, Javier

2006-02-23

The transport equations of electrodiffusion processes use three reference frames for defining the fluxes: Fick's reference in diffusion, solvent-fixed reference in transference numbers, and laboratory fluxes in electric conductivity. The convenience of using only one reference frame is analyzed here from the point of view of the thermodynamics of irreversible processes. A relation between the fluxes of ions and solvent and the electric current density is deduced first from a mass and volume balance. This is then used to show that (i) the laboratory and Fick's diffusion coefficients are identical and (ii) the transference numbers of both the solvent and the ion in the laboratory reference frame are related. Finally, four experimental methods for the measurement of ion transference numbers are analyzed critically. New expressions for evaluating transference numbers for the moving boundary method and the chronopotentiometry technique are deduced. It is concluded that the ion transport equation in the laboratory reference frame plays a key role in the description of electrodiffusion processes.

Stoichiometric sensing to opt between gelation and crystallization.

PubMed

Vidyasagar, Adiyala; Sureshan, Kana M

2015-10-05

A new class of organogelators having a cyclohexane-1a,3a-diol motif capable of congealing non-polar liquids was developed. These gelators underwent crystallization at low concentration and gelation above the critical gelation concentration (CGC) in the same solvent. The crystals and gel fibers were analyzed by single crystal XRD and PXRD respectively, which revealed their different modes of assembly. The XRD studies and thermogravimetric analysis (TGA) confirmed that the crystals contain a water of crystallization whereas the gel fibers do not. A systematic study revealed that when the concentration of the gelator exceeds that of adventitious water in the solvent, it congeals the solvent and when the concentration of the gelator is less than water, it undergoes crystallization. This unprecedented stoichiometric sensing behavior in deciding the mode of self-assembly offers a handle to opt between mutually competing gelation and crystallization. We have confirmed that the system can be biased to congeal or crystallize by varying the amount of water. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Competitive photocyclization/rearrangement of 4-aryl-1,1-dicyanobutenes controlled by intramolecular charge-transfer interaction. Effect of medium polarity, temperature, pressure, excitation wavelength, and confinement.

PubMed

Ito, Tadashi; Nishiuchi, Emi; Fukuhara, Gaku; Inoue, Yoshihisa; Mori, Tadashi

2011-09-01

A series of 4-aryl-1,1-dicyanobutenes (1a-1f) with different substituents were synthesized to control the intramolecular donor-acceptor or charge-transfer (C-T) interactions in the ground state. Photoexcitation of these C-T substrates led to competitive cyclization and rearrangement, the ratio being critically controlled by various environmental factors, such as solvent polarity, temperature and static pressure, and also by excitation wavelength and supramolecular confinement (polyethylene voids). In non-polar solvents, the rearrangement was dominant (>10 : 1) for all examined substrates, while the cyclization was favoured in polar solvents, in particular at low temperatures. Selective excitation at the C-T band further enhanced the cyclization up to >50 : 1 ratios. More importantly, the cyclization/rearrangement ratio was revealed to be a linear function of the C-T transition energy. However, the substrates with a sterically demanding or highly electron-donating substituent failed to give the cyclization product.

Free energy landscape for glucose condensation and dehydration reactions in dimethyl sulfoxide and the effects of solvent.

PubMed

Qian, Xianghong; Liu, Dajiang

2014-03-31

The mechanisms and free energy surfaces (FES) for the initial critical steps during proton-catalyzed glucose condensation and dehydration reactions were elucidated in dimethyl sulfoxide (DMSO) using Car-Parrinello molecular dynamics (CPMD) coupled with metadynamics (MTD) simulations. Glucose condensation reaction is initiated by protonation of C1--OH whereas dehydration reaction is initiated by protonation of C2--OH. The mechanisms in DMSO are similar to those in aqueous solution. The DMSO molecules closest to the C1--OH or C2--OH on glucose are directly involved in the reactions and act as proton acceptors during the process. However, the energy barriers are strongly solvent dependent. Moreover, polarization from the long-range electrostatic interaction affects the mechanisms and energetics of glucose reactions. Experimental measurements conducted in various DMSO/Water mixtures also show that energy barriers are solvent dependent in agreement with our theoretical results. Copyright © 2014 Elsevier Ltd. All rights reserved.

MARE CLEAN 200

EPA Pesticide Factsheets

Technical product bulletin: this solvent-based dispersant for oil spill cleanups is not affected by salinity, and is effective on any liquid hydrocarbon. Solvent is paraffinic hydrocarbons, surfactants include sorbitan fatty acid esters and polysorbates.

Switchable solvents and methods of use thereof

DOEpatents

Jessop, Philip G.; Eckert, Charles A.; Liotta, Charles L.; Heldebrant, David J.

2013-08-20

A solvent that reversibly converts from a nonionic liquid mixture to an ionic liquid upon contact with a selected trigger, e.g., contact with CO.sub.2, is described. In preferred embodiments, the ionic solvent is readily converted back to the nonionic liquid mixture. The nonionic liquid mixture includes an amidine or guanidine or both, and water, alcohol, or a combination thereof. Single component amine solvents that reversibly convert between ionic and non-ionic states are also described. Some embodiments require increased pressure to convert; others convert at 1 atmosphere.

Switchable solvents and methods of use thereof

DOEpatents

Jessop, Philip G [Kingston, CA; Eckert, Charles A [Atlanta, GA; Liotta, Charles L [Atlanta, GA; Heldebrant, David J [Richland, WA

2011-07-19

A solvent that reversibly converts from a nonionic liquid mixture to an ionic liquid upon contact with a selected trigger, e.g., contact with CO.sub.2, is described. In preferred embodiments, the ionic solvent is readily converted back to the nonionic liquid mixture. The nonionic liquid mixture includes an amidine or guanidine or both, and water, alcohol, or a combination thereof. Single component amine solvents that reversibly convert between ionic and non-ionic states are also described. Some embodiments require increased pressure to convert; others convert at 1 atmosphere.

Switchable solvents and methods of use thereof

DOEpatents

Jessop, Philip G; Eckert, Charles A; Liotta, Charles L; Heldebrant, David J

2014-04-29

A solvent that reversibly converts from a nonionic liquid mixture to an ionic liquid upon contact with a selected trigger, e.g., contact with CO.sub.2, is described. In preferred embodiments, the ionic solvent is readily converted back to the nonionic liquid mixture. The nonionic liquid mixture includes an amidine or guanidine or both, and water, alcohol, or a combination thereof. Single component amine solvents that reversibly convert between ionic and non-ionic states are also described. Some embodiments require increased pressure to convert; others convert at 1 atmosphere.

Dopant ink composition and method of fabricating a solar cell there from

DOEpatents

Loscutoff, Paul; Wu, Kahn; Molesa, Steven Edward

2017-10-25

Dopant ink compositions and methods of fabricating solar cells there from are described. A dopant ink composition may include a cross-linkable matrix precursor, a bound dopant species, and a solvent. A method of fabricating a solar cell may include delivering a dopant ink composition to a region above a substrate. The dopant ink composition includes a cross-linkable matrix precursor, a bound dopant species, and a solvent. The method also includes baking the dopant ink composition to remove a substantial portion of the solvent of the dopant ink composition, curing the baked dopant ink composition to cross-link a substantial portion of the cross-linkable matrix precursor of the dopant ink composition, and driving dopants from the cured dopant ink composition toward the substrate.

Dopant ink composition and method of fabricating a solar cell there from

DOEpatents

Loscutoff, Paul; Wu, Kahn; Molesa, Steven Edward

2015-03-31

Dopant ink compositions and methods of fabricating solar cells there from are described. A dopant ink composition may include a cross-linkable matrix precursor, a bound dopant species, and a solvent. A method of fabricating a solar cell may include delivering a dopant ink composition to a region above a substrate. The dopant ink composition includes a cross-linkable matrix precursor, a bound dopant species, and a solvent. The method also includes baking the dopant ink composition to remove a substantial portion of the solvent of the dopant ink composition, curing the baked dopant ink composition to cross-link a substantial portion of the cross-linkable matrix precursor of the dopant ink composition, and driving dopants from the cured dopant ink composition toward the substrate.

Experimental Limiting Oxygen Concentrations for Nine Organic Solvents at Temperatures and Pressures Relevant to Aerobic Oxidations in the Pharmaceutical Industry

PubMed Central

2015-01-01

Applications of aerobic oxidation methods in pharmaceutical manufacturing are limited in part because mixtures of oxygen gas and organic solvents often create the potential for a flammable atmosphere. To address this issue, limiting oxygen concentration (LOC) values, which define the minimum partial pressure of oxygen that supports a combustible mixture, have been measured for nine commonly used organic solvents at elevated temperatures and pressures. The solvents include acetic acid, N-methylpyrrolidone, dimethyl sulfoxide, tert-amyl alcohol, ethyl acetate, 2-methyltetrahydrofuran, methanol, acetonitrile, and toluene. The data obtained from these studies help define safe operating conditions for the use of oxygen with organic solvents. PMID:26622165

Improved strategies for DNP-enhanced 2D 1 H-X heteronuclear correlation spectroscopy of surfaces

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

Kobayashi, Takeshi; Perras, Frederic A.; Chaudhary, Umesh

We demonstrate that dynamic nuclear polarization (DNP)-enhanced 1H-X heteronuclear correlation (HETCOR) measurements of hydrogen-rich surface species are better accomplished by using proton-free solvents. This approach notably prevents HETCOR spectra from being obfuscated by the solvent-derived signals otherwise present in DNP measurements. Additionally, in the hydrogen-rich materials studied here, which included functionalized mesoporous silica nanoparticles and metal organic frameworks, the use of proton-free solvents afforded higher sensitivity gains than the commonly used solvents containing protons. Here, we also explored the possibility of using a solvent-free sample formulation and the feasibility of indirect detection in DNP-enhanced HETCOR experiments.

Solvent for urethane adhesives and coatings and method of use

DOEpatents

Simandl, Ronald F.; Brown, John D.; Holt, Jerrid S.

2010-08-03

A solvent for urethane adhesives and coatings, the solvent having a carbaldehyde and a cyclic amide as constituents. In some embodiments the solvent consists only of miscible constituents. In some embodiments the carbaldehyde is benzaldehyde and in some embodiments the cyclic amide is N-methylpyrrolidone (M-pyrole). An extender may be added to the solvent. In some embodiments the extender is miscible with the other ingredients, and in some embodiments the extender is non-aqueous. For example, the extender may include isopropanol, ethanol, tetrahydro furfuryl alcohol, benzyl alcohol, Gamma-butyrolactone or a caprolactone. In some embodiments a carbaldehyde and a cyclic amide are heated and used to separate a urethane bonded to a component.

Improved strategies for DNP-enhanced 2D 1 H-X heteronuclear correlation spectroscopy of surfaces

DOE PAGES

Kobayashi, Takeshi; Perras, Frederic A.; Chaudhary, Umesh; ...

2017-08-12

We demonstrate that dynamic nuclear polarization (DNP)-enhanced 1H-X heteronuclear correlation (HETCOR) measurements of hydrogen-rich surface species are better accomplished by using proton-free solvents. This approach notably prevents HETCOR spectra from being obfuscated by the solvent-derived signals otherwise present in DNP measurements. Additionally, in the hydrogen-rich materials studied here, which included functionalized mesoporous silica nanoparticles and metal organic frameworks, the use of proton-free solvents afforded higher sensitivity gains than the commonly used solvents containing protons. Here, we also explored the possibility of using a solvent-free sample formulation and the feasibility of indirect detection in DNP-enhanced HETCOR experiments.

Enabling technologies and green processes in cyclodextrin chemistry.

PubMed

Cravotto, Giancarlo; Caporaso, Marina; Jicsinszky, Laszlo; Martina, Katia

2016-01-01

The design of efficient synthetic green strategies for the selective modification of cyclodextrins (CDs) is still a challenging task. Outstanding results have been achieved in recent years by means of so-called enabling technologies, such as microwaves, ultrasound and ball mills, that have become irreplaceable tools in the synthesis of CD derivatives. Several examples of sonochemical selective modification of native α-, β- and γ-CDs have been reported including heterogeneous phase Pd- and Cu-catalysed hydrogenations and couplings. Microwave irradiation has emerged as the technique of choice for the production of highly substituted CD derivatives, CD grafted materials and polymers. Mechanochemical methods have successfully furnished greener, solvent-free syntheses and efficient complexation, while flow microreactors may well improve the repeatability and optimization of critical synthetic protocols.

Method for synthesizing metal bis(borano) hypophosphite complexes

DOEpatents

Cordaro, Joseph G.

2013-06-18

The present invention describes the synthesis of a family of metal bis(borano) hypophosphite complexes. One procedure described in detail is the syntheses of complexes beginning from phosphorus trichloride and sodium borohydride. Temperature, solvent, concentration, and atmosphere are all critical to ensure product formation. In the case of sodium bis(borano) hypophosphite, hydrogen gas was evolved upon heating at temperatures above 150.degree. C. Included in this family of materials are the salts of the alkali metals Li, Na and K, and those of the alkaline earth metals Mg and Ca. Hydrogen storage materials are possible. In particular the lithium salt, Li[PH.sub.2(BH.sub.3).sub.2], theoretically would contain nearly 12 wt % hydrogen. Analytical data for product characterization and thermal properties are given.

Method for molding ceramic powders

DOEpatents

Janney, Mark A.

1990-01-01

A method for molding ceramic powders comprises forming a slurry mixture including ceramic powder, a dispersant for the metal-containing powder, and a monomer solution. The monomer solution includes at least one multifunctional monomer, a free-radical initiator, and an organic solvent. The slurry mixture is transferred to a mold, and the mold containing the slurry mixture is heated to polymerize and crosslink the monomer and form a firm polymer-solvent gel matrix. The solid product may be removed from the mold and heated to first remove the solvent and subsequently remove the polymer, whereafter the product may be sintered.

Method for molding ceramic powders

DOEpatents

Janney, M.A.

1990-01-16

A method for molding ceramic powders comprises forming a slurry mixture including ceramic powder, a dispersant for the metal-containing powder, and a monomer solution. The monomer solution includes at least one multifunctional monomer, a free-radical initiator, and an organic solvent. The slurry mixture is transferred to a mold, and the mold containing the slurry mixture is heated to polymerize and crosslink the monomer and form a firm polymer-solvent gel matrix. The solid product may be removed from the mold and heated to first remove the solvent and subsequently remove the polymer, where after the product may be sintered.

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

Assigning exposure to pesticides and solvents from self-reports collected by a computer assisted personal interview and expert assessment of job codes: the UK Adult Brain Tumour Study.

PubMed

Hepworth, S J; Bolton, A; Parslow, R C; van Tongeren, M; Muir, K R; McKinney, P A

2006-04-01

To compare assignment of occupational pesticide and solvent exposure using self-reported data collected by a computer assisted personal interview (CAPI) with exposure based on expert assessment of job codes. To discuss the advantages and disadvantages of using a CAPI to collect individual occupational exposure data. Between 2001 and 2004, 1495 participants were interviewed using a CAPI for a case-control study of adult brain tumours and acoustic neuromas. Two types of occupational data were collected: (1) a full history, including job title from which a job code was assigned from the Standard Occupational Classification; and (2) specific details on pesticide and solvent exposure reported by participants. Study members' experiences of using the CAPI were recorded and advantages and disadvantages summarised. Of 7192 jobs recorded, the prevalence of self-reported exposure was 1.3% for pesticides and 11.5% for solvents. Comparing this with exposure expertly assessed from job titles showed 53.6% and 45.8% concordance for pesticides and solvents respectively. Advantages of the CAPI include no data entry stage, automatic input validation, and a reduction in interviewer bias. Disadvantages include an adverse effect on study implementation as a consequence of resources required for programming and difficulties encountered with data management prior to analysis. Different methods of exposure assessment derive different exposure levels for pesticide and solvent exposure at work. Agreement between self-reported and expert assessment of exposure was greater for pesticides compared to solvents. The advantages of using a CAPI for the collection of complex data outweigh the disadvantages for interviewers and data quality but using such a method requires extra resources at the study outset.

Assigning exposure to pesticides and solvents from self‐reports collected by a computer assisted personal interview and expert assessment of job codes: the UK Adult Brain Tumour Study

PubMed Central

Hepworth, S J; Bolton, A; Parslow, R C; van Tongeren, M; Muir, K R; McKinney, P A

2006-01-01

Objectives To compare assignment of occupational pesticide and solvent exposure using self‐reported data collected by a computer assisted personal interview (CAPI) with exposure based on expert assessment of job codes. To discuss the advantages and disadvantages of using a CAPI to collect individual occupational exposure data. Methods Between 2001 and 2004, 1495 participants were interviewed using a CAPI for a case‐control study of adult brain tumours and acoustic neuromas. Two types of occupational data were collected: (1) a full history, including job title from which a job code was assigned from the Standard Occupational Classification; and (2) specific details on pesticide and solvent exposure reported by participants. Study members' experiences of using the CAPI were recorded and advantages and disadvantages summarised. Results Of 7192 jobs recorded, the prevalence of self‐reported exposure was 1.3% for pesticides and 11.5% for solvents. Comparing this with exposure expertly assessed from job titles showed 53.6% and 45.8% concordance for pesticides and solvents respectively. Advantages of the CAPI include no data entry stage, automatic input validation, and a reduction in interviewer bias. Disadvantages include an adverse effect on study implementation as a consequence of resources required for programming and difficulties encountered with data management prior to analysis. Conclusions Different methods of exposure assessment derive different exposure levels for pesticide and solvent exposure at work. Agreement between self‐reported and expert assessment of exposure was greater for pesticides compared to solvents. The advantages of using a CAPI for the collection of complex data outweigh the disadvantages for interviewers and data quality but using such a method requires extra resources at the study outset. PMID:16556747

Solvent effects on adsorption of CO over CuCl(1 1 1) surface: A density functional theory study

NASA Astrophysics Data System (ADS)

Zhang, Riguang; Ling, Lixia; Wang, Baojun; Huang, Wei

2010-09-01

DFT calculations have been performed to investigate the effect of dielectric responses of the solvent environment on the CO adsorption over CuCl(1 1 1) surface by using COSMO (conductor-like solvent model) model in Dmol 3. Different dielectric constants, including vacuum, liquid paraffin, methylene chloride, methanol and water solution, are considered. The effects of solvent model on the structural parameters, adsorption energies and vibrational frequency of CO adsorption over CuCl(1 1 1) surface have been investigated. The calculation results suggest that solvent effects can improve the stability of CO adsorption and reduce the intensity of C-O bond, which might mean that solvent is in favor of C-O bond activation and improve the reaction activity of oxidative carbonylation in a slurry reactor.

Organic solvent pretreatment of lignocellulosic biomass for biofuels and biochemicals: A review.

PubMed

Zhang, Ke; Pei, Zhijian; Wang, Donghai

2016-01-01

Lignocellulosic biomass represents the largest potential volume and lowest cost for biofuel and biochemical production. Pretreatment is an essential component of biomass conversion process, affecting a majority of downstream processes, including enzymatic hydrolysis, fermentation, and final product separation. Organic solvent pretreatment is recognized as an emerging way ahead because of its inherent advantages, such as the ability to fractionate lignocellulosic biomass into cellulose, lignin, and hemicellulose components with high purity, as well as easy solvent recovery and solvent reuse. Objectives of this review were to update and extend previous works on pretreatment of lignocellulosic biomass for biofuels and biochemicals using organic solvents, especially on ethanol, methanol, ethylene glycol, glycerol, acetic acid, and formic acid. Perspectives and recommendations were given to fully describe implementation of proper organic solvent pretreatment for future research. Copyright © 2015 Elsevier Ltd. All rights reserved.

Preparation of B-trichloroborazine

NASA Technical Reports Server (NTRS)

Riccitiello, Salvatore R.; Hsu, Ming-Ta S.; Chen, Timothy S.

1987-01-01

The present invention relates to a method of preparing B-trichloroborazine. Generally, the method includes the combination of gaseous boron trichloride in an anhydrous aprotic organic solvent followed by addition of excess gaseous ammonia at ambient temperature or below. The reaction mixture is heated to about 100 to 140 C followed by cooling, removal of the solid ammonium chloride at ambient temperature, distillation of the solvent under vacuum if necessary at a temperature of up to about 112 C, and recovery of the B-trichloroborazine. Solvents include toluene, benzene, xylene, chlorinated hydrocarbons, chlorinated aromatic compounds, or mixtures thereof. Toluene is a preferred solvent. The process provides a convenient synthesis of a material which often decomposes on standing. B-trichloroborazine is useful in a number of chemical reactions, and particularly in the formation of high temperature inorganic polymers and polymer precursors.

Electrospinning cellulose based nanofibers for sensor applications

NASA Astrophysics Data System (ADS)

Nartker, Steven

2009-12-01

Bacterial pathogens have recently become a serious threat to the food and water supply. A biosensor based on an electrochemical immunoassay has been developed for detecting food borne pathogens, such as Escherichia coli (E. coli) O157:H7. These sensors consist of several materials including, cellulose, cellulose nitrate, polyaniline and glass fibers. The current sensors have not been optimized in terms of microscale architecture and materials. The major problem associated with the current sensors is the limited concentration range of pathogens that provides a linear response on the concentration conductivity chart. Electrospinning is a process that can be used to create a patterned fiber mat design that will increase the linear range and lower the detection limit of these sensors by improving the microscale architecture. Using the electrospinning process to produce novel mats of cellulose nitrate will offer improved surface area, and the cellulose nitrate can be treated to further improve chemical interactions required for sensor activity. The macro and micro architecture of the sensor is critical to the performance of the sensors. Electrospinning technology can be used to create patterned architectures of nanofibers that will enhance sensor performance. To date electrospinning of cellulose nitrate has not been performed and optimization of the electrospinning process will provide novel materials suitable for applications such as filtration and sensing. The goal of this research is to identify and elucidate the primary materials and process factors necessary to produce cellulose nitrate nanofibers using the electrospinning process that will improve the performance of biosensors. Cellulose nitrate is readily dissolved in common organic solvents such as acetone, tetrahydrofuran (THF) and N,N dimethylformamide (DMF). These solvents can be mixed with other latent solvents such as ethanol and other alcohols to provide a solvent system with good electrospinning behavior. Using cellulose nitrate in biosensor materials provides excellent antibody binding characteristics that are resistant to pH changes. Sensors will be constructed of electrospun materials and compared to existing materials. The main advantage of electrospinning fiber mats is the increased surface area, and controllable morphology, which ultimately affects biosensor performance. Characterization tools will include Environmental Scanning Electron Microscopy (ESEM), BET N2 adsorption, X-Ray Photoelectron Spectroscopy (XPS), Dynamic Mechanical Analysis (DMA) and AC impedance.

Challenging Times: California Schools Cope with Adversity and the Imperative to Do More

ERIC Educational Resources Information Center

Edwards, Brian

2010-01-01

California school districts are being expected to "do more with less." They face critical and competing pressures to improve academic achievement while remaining fiscally solvent in a time of increasing budgetary pressures. This report examines the financial circumstances of California's school districts and the actions they have been…

Study on the disparate transition behaviors of the electrical/physical properties in PEDOT:PSS film depending on solvent species under a follow-up solution-treatment process

NASA Astrophysics Data System (ADS)

Yun, Dong-Jin; Kim, Jung-Hwa; Kim, Seong Heon; Seol, Minsu; Yu, DaEun; Kwon, Hyukju; Ham, Yongnam; Chung, JaeGwan; Kim, Yongsu; Heo, Sung

2016-04-01

In most solution-processed organic devices, a poly(3,4-ethylenedioxythiophene) (PEDOT) polymerized with poly(4-styrenesulfonate) (PSS) film is inevitably affected by various conditions during the subsequent solution-coating processes. To investigate the effects of direct solvent exposure on the properties of PEDOT polymerized with PSS (PEDOT:PSS) films, photoemission spectroscopy-based analytical methods were used before and after solvent-coating processes. Our results clearly indicate that PEDOT:PSS films undergo a different transition mechanism depending on the solubility of the solvent in water. The water-miscible solvents induce the solvation of hydrophilic PSS chains. As a result, this process allows the solvent to diffuse into the PEDOT:PSS film, and a conformational change between PEDOT and PSS occurs. On the other hand, the water-immiscible organic solvents cause the partial adsorption of solvent molecules at the PE surface, which leads to changes in the surface properties, including work function. Based on our finding, we demonstrate that the energy-level alignments at the organic semiconductor/electrode interface for the PEDOT:PSS films can be controlled by simple solvent treatments.

Preparation and characterization of superfine ammonium perchlorate (AP) crystals through ceramic membrane anti-solvent crystallization

NASA Astrophysics Data System (ADS)

Ma, Zhenye; Li, Cheng; Wu, Rujun; Chen, Rizhi; Gu, Zhenggui

2009-10-01

In this paper, a novel ceramic membrane anti-solvent crystallization (CMASC) method was proposed for the safe and rapid preparation ammonium perchlorate (AP) crystals, in which the acetone and ethyl acetate were chosen as solvent and anti-solvent, respectively. Comparing with the conventional liquid anti-solvent crystallization (LASC), CMASC which successfully introduces ceramic membrane with regular pore structure to the LASC as feeding medium, is favorable to control the rate of feeding rate and, therefore, to obtain size and morphology controllable AP. Several kinds of micro-sized AP particles with different morphology were obtained including polyhedral-like, quadrate-like to rod-like. The effect of processing parameters on the crystal size and shape of AP crystals such as volume ratio of anti-solvent to solvent, feeding pressure and crystallization temperature were investigated. It is found that higher volume ratio of anti-solvent to solvent, higher feeding pressure and higher temperature result in smaller particle size. Scaning electron microscopy (SEM) and X-ray diffraction (XRD) were used to characterize the resulting AP crystals. The nucleation and growth kinetic of the resulting AP crystals were also discussed.

Quantitative analysis of intramolecular exciplex and electron transfer in a double-linked zinc porphyrin-fullerene dyad.

PubMed

Al-Subi, Ali Hanoon; Niemi, Marja; Tkachenko, Nikolai V; Lemmetyinen, Helge

2012-10-04

Photoinduced charge transfer in a double-linked zinc porphyrin-fullerene dyad is studied. When the dyad is excited at the absorption band of the charge-transfer complex (780 nm), an intramolecular exciplex is formed, followed by the complete charge separated (CCS) state. By analyzing the results obtained from time-resolved transient absorption and emission decay measurements in a range of solvents with different polarities, we derived a dependence between the observable lifetimes and internal parameters controlling the reaction rate constants based on the semiquantum Marcus electron-transfer theory. The critical value of the solvent polarity was found to be ε(r) ≈ 6.5: in solvents with higher dielectric constants, the energy of the CCS state is lower than that of the exciplex and the relaxation takes place via the CCS state predominantly, whereas in solvents with lower polarities the energy of the CCS state is higher and the exciplex relaxes directly to the ground state. In solvents with moderate polarities the exciplex and the CCS state are in equilibrium and cannot be separated spectroscopically. The degree of the charge shift in the exciplex relative to that in the CCS state was estimated to be 0.55 ± 0.02. The electronic coupling matrix elements for the charge recombination process and for the direct relaxation of the exciplex to the ground state were found to be 0.012 ± 0.001 and 0.245 ± 0.022 eV, respectively.

Molecular dynamics simulation of solute diffusion in Lennard-Jones fluids

NASA Astrophysics Data System (ADS)

Yamaguchi, T.; Kimura, Y.; Hirota, N.

We performed a molecular dynamics (MD) simulation for a system of 5 solute molecules in 495 solvent molecules interacting through the Lennard-Jones (LJ) 12-6 potential, in order to study solvent density effects on the diffusion coefficients in supercritical fluids. The effects of the size of the solute and the strength of the solute-solvent attractive interaction on the diffusion coefficient of the solute were examined. The diffusion coefficients of the solute molecules were calculated at T = 1.5 (in the LJ reduced unit), slightly above the critical temperature, from rho = 0.1 to rho = 0.95, where rho is the number density in the LJ reduced unit. The memory function in the generalized Langevin equation was calculated, in order to know the molecular origin of the friction on a solute. The memory function is separated into fast and slow components. The former arises from the solute-solvent repulsive interaction, and is interpreted as collisional Enskog-like friction. The interaction strength dependence of the collisional friction is larger in the low- and medium-density regions, which is consistent with the 'clustering' picture, i.e., the local density enhancement due to the solute-solvent attractive interaction. However, the slow component of the memory function suppresses the effect of the local density on the diffusion coefficients, and as a result the effect of the attractive interaction is smaller on the diffusion coefficients than on the local density. Nonetheless, the solvent density dependence of the effect of the attraction on the diffusion coefficient varies with the local density, and it is concluded that the local density is the principal factor that determines the interaction strength dependence of the diffusion coefficient in the low- and medium-density regions (p < 0.6).

Determination of low methylmercury concentrations in peat soil samples by isotope dilution GC-ICP-MS using distillation and solvent extraction methods.

PubMed

Pietilä, Heidi; Perämäki, Paavo; Piispanen, Juha; Starr, Mike; Nieminen, Tiina; Kantola, Marjatta; Ukonmaanaho, Liisa

2015-04-01

Most often, only total mercury concentrations in soil samples are determined in environmental studies. However, the determination of extremely toxic methylmercury (MeHg) in addition to the total mercury is critical to understand the biogeochemistry of mercury in the environment. In this study, N2-assisted distillation and acidic KBr/CuSO4 solvent extraction methods were applied to isolate MeHg from wet peat soil samples collected from boreal forest catchments. Determination of MeHg was performed using a purge and trap GC-ICP-MS technique with a species-specific isotope dilution quantification. Distillation is known to be more prone to artificial MeHg formation compared to solvent extraction which may result in the erroneous MeHg results, especially with samples containing high amounts of inorganic mercury. However, methylation of inorganic mercury during the distillation step had no effect on the reliability of the final MeHg results when natural peat soil samples were distilled. MeHg concentrations determined in peat soil samples after distillation were compared to those determined after the solvent extraction method. MeHg concentrations in peat soil samples varied from 0.8 to 18 μg kg(-1) (dry weight) and the results obtained with the two different methods did not differ significantly (p=0.05). The distillation method with an isotope dilution GC-ICP-MS was shown to be a reliable method for the determination of low MeHg concentrations in unpolluted soil samples. Furthermore, the distillation method is solvent-free and less time-consuming and labor-intensive when compared to the solvent extraction method. Copyright © 2014 Elsevier Ltd. All rights reserved.

1H NMR-based metabolomics reveals interactive effects between the carrier solvent methanol and a pharmaceutical mixture in an amphibian developmental bioassay with Limnodynastes peronii.

PubMed

Melvin, Steven D; Jones, Oliver A H; Carroll, Anthony R; Leusch, Frederic D L

2018-05-01

Organic carrier solvents are used in aquatic toxicity testing to improve chemical solubility and facilitate the exploration of dose-response relationships. Both water- and solvent-control groups are normally included in these scenarios to ensure that the solvent itself has no effect on the test organism, but this fails to consider possible interactive effects between carrier solvents and contaminants of interest. We explored this topic by exposing Limnodynastes peronii tadpoles to a mixture of common water-soluble pharmaceuticals (diclofenac, metformin and valproic acid) in the presence and absence of the carrier solvent methanol, according to standard developmental bioassay methodology. Nuclear Magnetic Resonance (NMR) spectroscopy was applied as a platform for untargeted metabolomics, to compare broad sub-lethal hepatotoxicity in solvent- and solvent-free exposure scenarios. Considerable interactive effects were identified between the pharmaceutical mixture and a typical dose of methanol (0.003%). Specifically, pronounced differences were observed between the solvent- and solvent-free exposure groups for leucine, acetate, glutamine, citrate, glycogen, tyrosine, arginine, purine nucleotides and an unidentified metabolite at 6.53 ppm. Various other metabolites exhibited similar disparity related to the use of carrier solvent, but the interactions were non-significant. These results raise important questions about the use of carrier solvents for chemical exposures in aquatic ecotoxicology, and particularly for studies interested in sub-lethal mechanistic information and/or biomarker discovery. Copyright © 2018 Elsevier Ltd. All rights reserved.

Coated electroactive materials

DOEpatents

Amine, Khalil; Abouimrane, Ali

2016-08-30

A process includes suspending an electroactive material in a solvent, suspending or dissolving a carbon precursor in the solvent; and depositing the carbon precursor on the electroactive material to form a carbon-coated electroactive material. Compositions include a graphene-coated electroactive material prepared from a solution phase mixture or suspension of an electroactive material and graphene, graphene oxide, or a mixture thereof.

Absorption Spectra and Photoreactivity of p-Aminobenzophenone by Time-dependent Density Functional Theory

NASA Astrophysics Data System (ADS)

Cheng, Xue-mei; Huang, Yao; Ma, Jian-yi; Li, Xiang-yuan

2007-06-01

The absorption spectral properties of para-aminobenzophenone (p-ABP) were investigated in gas phase and in solution by time-dependent density functional theory. Calculations suggest that the singlet states vary greatly with the solvent polarities. In various polar solvents, including acetonitrile, methanol, ethanol, dimethyl sulfoxide, and dimethyl formamide, the excited S1 states with charge transfer character result from π → π* transitions. However, in nonpolar solvents, cyclohexane, and benzene, the S1 states are the result of n → π* transitions related to local excitation in the carbonyl group. The excited T1 states were calculated to have ππ* character in various solvents. From the variation of the calculated excited states, the band due to π → π* transition undergoes a redshift with an increase in solvent polarity, while the band due to n → π* transition undergoes a blueshift with an increase in solvent polarity. In addition, the triplet yields and the photoreactivities of p-ABP in various solvents are discussed.

Quantification of Structural Isomers via Mode-Selective Irmpd

NASA Astrophysics Data System (ADS)

Polfer, Nicolas C.

2016-06-01

Mixtures of structural isomers can pose a challenge for vibrational ion spectroscopy. In cases where particular structures display diagnostic vibrations, these structures can be selectively "burned away". In ion traps, the ion population can be subjected to multiple laser shots, in order to fully deplete a particular structure, in effect allowing a quantification of this structure. Protonated para-amino benzoic acid (PABA) serves as an illustrative example. PABA is known to preferentially exist in the N-protonated (N-prot) form in solution, but in the gas phase it is energetically favorable in the O-protonated (O-prot) form. As shown in Figure 1, the N-prot structure can be kinetically trapped in the gas phase when sprayed from non-protic solvent, whereas the O-prot structure is obtained when sprayed from protic solvents, analogous to results by others [1,2]. y parking the light source on the diagnostic 3440 wn mode, the percentage of the O-prot structure can be determined, and by default the remainder is assumed to adopt the N-prot structure. It will be shown that the relative percentages of O-prot vs N-prot are highly dependent on the solvent mixture, going from close to 0% O-prot in non-protic solvents, to 99% in protic solvents. Surprisingly, water behaves much more like a non-protic solvent than methanol. It is observed that the capillary temperature, which aids droplet desolvation by black-body radiation in the ESI source, is critical to promote the appearance of O-prot structures. These results are consistent with the picture that a protic bridge mechanism is at play to facilitate proton transfer, and thus allow conversion from N-prot to O-prot, but that this mechanism is subject to appreciable kinetic barriers on the timescale of solvent evaporation. 1. J. Phys. Chem. A 2011, 115, 7625. 2. Anal. Chem. 2012, 84, 7857.

Connecting Free Energy Surfaces in Implicit and Explicit Solvent: an Efficient Method to Compute Conformational and Solvation Free Energies

PubMed Central

Deng, Nanjie; Zhang, Bin W.; Levy, Ronald M.

2015-01-01

The ability to accurately model solvent effects on free energy surfaces is important for understanding many biophysical processes including protein folding and misfolding, allosteric transitions and protein-ligand binding. Although all-atom simulations in explicit solvent can provide an accurate model for biomolecules in solution, explicit solvent simulations are hampered by the slow equilibration on rugged landscapes containing multiple basins separated by barriers. In many cases, implicit solvent models can be used to significantly speed up the conformational sampling; however, implicit solvent simulations do not fully capture the effects of a molecular solvent, and this can lead to loss of accuracy in the estimated free energies. Here we introduce a new approach to compute free energy changes in which the molecular details of explicit solvent simulations are retained while also taking advantage of the speed of the implicit solvent simulations. In this approach, the slow equilibration in explicit solvent, due to the long waiting times before barrier crossing, is avoided by using a thermodynamic cycle which connects the free energy basins in implicit solvent and explicit solvent using a localized decoupling scheme. We test this method by computing conformational free energy differences and solvation free energies of the model system alanine dipeptide in water. The free energy changes between basins in explicit solvent calculated using fully explicit solvent paths agree with the corresponding free energy differences obtained using the implicit/explicit thermodynamic cycle to within 0.3 kcal/mol out of ~3 kcal/mol at only ~8 % of the computational cost. We note that WHAM methods can be used to further improve the efficiency and accuracy of the explicit/implicit thermodynamic cycle. PMID:26236174

Connecting free energy surfaces in implicit and explicit solvent: an efficient method to compute conformational and solvation free energies.

PubMed

Deng, Nanjie; Zhang, Bin W; Levy, Ronald M

2015-06-09

The ability to accurately model solvent effects on free energy surfaces is important for understanding many biophysical processes including protein folding and misfolding, allosteric transitions, and protein–ligand binding. Although all-atom simulations in explicit solvent can provide an accurate model for biomolecules in solution, explicit solvent simulations are hampered by the slow equilibration on rugged landscapes containing multiple basins separated by barriers. In many cases, implicit solvent models can be used to significantly speed up the conformational sampling; however, implicit solvent simulations do not fully capture the effects of a molecular solvent, and this can lead to loss of accuracy in the estimated free energies. Here we introduce a new approach to compute free energy changes in which the molecular details of explicit solvent simulations are retained while also taking advantage of the speed of the implicit solvent simulations. In this approach, the slow equilibration in explicit solvent, due to the long waiting times before barrier crossing, is avoided by using a thermodynamic cycle which connects the free energy basins in implicit solvent and explicit solvent using a localized decoupling scheme. We test this method by computing conformational free energy differences and solvation free energies of the model system alanine dipeptide in water. The free energy changes between basins in explicit solvent calculated using fully explicit solvent paths agree with the corresponding free energy differences obtained using the implicit/explicit thermodynamic cycle to within 0.3 kcal/mol out of ∼3 kcal/mol at only ∼8% of the computational cost. We note that WHAM methods can be used to further improve the efficiency and accuracy of the implicit/explicit thermodynamic cycle.

SOLVENT WASTE REDUCTION ALTERNATIVES

EPA Science Inventory

This publication contains edited versions of presentations on this subject made at five Technology Transfer seminars in 1988. Chapters are included on land disposal regulations and requirements; waste solvent disposal alternatives from various industries such as process equipment...

Electrolyte formulations

DOEpatents

Zhu, Ye; Strand, Deidre; Cheng, Gang

2018-05-29

An electrochemical cell including a silicon-based anode and an electrolyte, where the electrolyte is formulated to contain solvents having cyclic sulfone or cyclic sulfite chemical structure. Specific additional solvent and salt combinations yield superior performance in these electrochemical cells.

Ex vivo study of transdermal permeation of four diclofenac salts from different vehicles.

PubMed

Minghetti, Paola; Cilurzo, Francesco; Casiraghi, Antonella; Montanari, Luisa; Fini, Adamo

2007-04-01

The ex vivo permeation of diclofenac was studied using four different salts (sodium, potassium, diethylamine, and epolamine) dissolved in four different solvents (water, propylene glycol (PG), Transcutol, and oleic acid (OA)) as donor phases through a human skin membrane. The four salts show different solubility values and different behavior in the four solvents, which are also permeation enhancers and this fact further is connected to the permeation results. The same order of magnitude of fluxes through the membrane as those previously reported for acidic diclofenac released from buffer solutions of pH >7 were found, taking into account differences originated by different membranes and other parameters tested in the experiments. Saturation concentration for the four salts in different solvents, necessary to calculate permeation coefficients, was critically evaluated; a short discussion made it possible to explain that corrections in the solubility values must be considered, related to the complex behavior in solution of these salts. Statistical processing of the experimental data suggests that differences between the four salts in promoting absorption of the drug is unproven; while differences are evident between the solvents, water is the most effective enhancing vehicle. Aqueous formulations containing diclofenac salt with an organic base appear to be the best combination to promote permeation in topical applications. (c) 2007 Wiley-Liss, Inc.

Transferring pharmaceuticals into the gas phase

NASA Astrophysics Data System (ADS)

Christen, Wolfgang; Krause, Tim; Rademann, Klaus

2008-11-01

The dissolution of molecules of biological interest in supercritical carbon dioxide is investigated using pulsed molecular beam mass spectrometry. Due to the mild processing temperatures of most supercritical fluids, their adiabatic expansion into vacuum permits to transfer even thermally very sensitive substances into the gas phase, which is particularly attractive for pharmaceutical and biomedical applications. In addition, supercritical CO2constitutes a chemically inert solvent that is compatible with hydrocarbon-free ultrahigh vacuum conditions. Here, we report on the dissolution and pulsed supersonic jet expansion of caffeine (C8H10N4O2), the provitamin menadione (C11H8O2), and the amino acid derivative l-phenylalanine tert-butyl ester hydrochloride (C6H5CH2CH(NH2)COOC(CH3)3[dot operator]HCl), into vacuum. An on-axis residual gas analyzer is used to monitor the relative amounts of solute and solvent in the molecular beam as a function of solvent densityE The excellent selectivity and sensitivity provided by mass spectrometry permits to probe even trace amounts of solutes. The strong density variation of CO2 close to the critical point results in a pronounced pressure dependence of the relative ion currents of solute and solvent molecules, reflecting a substantial change in solubility.

Mechanistic Study of Electrolyte Additives to Stabilize High-Voltage Cathode-Electrolyte Interface in Lithium-Ion Batteries.

PubMed

Gao, Han; Maglia, Filippo; Lamp, Peter; Amine, Khalil; Chen, Zonghai

2017-12-27

Current developments of electrolyte additives to stabilize electrode-electrolyte interface in lithium-ion batteries highly rely on a trial-and-error search, which involves repetitive testing and intensive amount of resources. The lack of understandings on the fundamental protection mechanisms of the additives significantly increases the difficulty for the transformational development of new additives. In this study, we investigated two types of individual protection routes to build a robust cathode-electrolyte interphase at high potentials: (i) a direct reduction in the catalytic decomposition of the electrolyte solvent; and (ii) formation of a "corrosion inhibitor film" that prevents severely attack and passivation from protons that generated from the solvent oxidation, even the decomposition of solvent cannot be mitigated. Effect of two exemplary electrolyte additives, lithium difluoro(oxalato)borate (LiDFOB) and 3-hexylthiophene (3HT), on LiNi 0.6 Mn 0.2 Co 0.2 O 2 (NMC 622) cathode were investigated to validate our hypothesis. It is demonstrated that understandings of both electrolyte additives and solvent are essential and careful balance between the cathode protection mechanism of additives and their side effects is critical to obtain optimum results. More importantly, this study opens up new directions of rational design of functional electrolyte additives for the next-generation high-energy-density lithium-ion chemistries.

Solvatochromic Effects on the Absorption Spectrum of 2-Thiocytosine

PubMed Central

2017-01-01

The solvatochromic effects of six different solvents on the UV absorption spectrum of 2-thiocytosine have been studied by a combination of experimental and theoretical techniques. The steady-state absorption spectra show significant shifts of the absorption bands, where in more polar solvents the first absorption maximum shifts to higher transition energies and the second maximum to lower energies. The observed solvatochromic shifts have been rationalized using three popular solvatochromic scales and with high-level multireference quantum chemistry calculations including implicit and explicit solvent effects. It has been found that the dipole moments of the excited states account for some general shifts in the excitation energies, whereas the explicit solvent interactions explain the differences in the spectra recorded in the different solvents. PMID:28452483

Experimental limiting oxygen concentrations for nine organic solvents at temperatures and pressures relevant to aerobic oxidations in the pharmaceutical industry

DOE PAGES

Osterberg, Paul M.; Niemeier, Jeffry K.; Welch, Christopher J.; ...

2014-12-06

Applications of aerobic oxidation methods in pharmaceutical manufacturing are limited in part because mixtures of oxygen gas and organic solvents often create the potential for a flammable atmosphere. To address this issue, limiting oxygen concentration (LOC) values, which define the minimum partial pressure of oxygen that supports a combustible mixture, have been measured for nine commonly used organic solvents at elevated temperatures and pressures. The solvents include acetic acid, N-methylpyrrolidone, dimethyl sulfoxide, tert-amyl alcohol, ethyl acetate, 2-methyltetrahydrofuran, methanol, acetonitrile, and toluene. Furthermore, the data obtained from these studies help define safe operating conditions for the use of oxygen with organicmore » solvents.« less

MoleculaRnetworks: an integrated graph theoretic and data mining tool to explore solvent organization in molecular simulation.

PubMed

Mooney, Barbara Logan; Corrales, L René; Clark, Aurora E

2012-03-30

This work discusses scripts for processing molecular simulations data written using the software package R: A Language and Environment for Statistical Computing. These scripts, named moleculaRnetworks, are intended for the geometric and solvent network analysis of aqueous solutes and can be extended to other H-bonded solvents. New algorithms, several of which are based on graph theory, that interrogate the solvent environment about a solute are presented and described. This includes a novel method for identifying the geometric shape adopted by the solvent in the immediate vicinity of the solute and an exploratory approach for describing H-bonding, both based on the PageRank algorithm of Google search fame. The moleculaRnetworks codes include a preprocessor, which distills simulation trajectories into physicochemical data arrays, and an interactive analysis script that enables statistical, trend, and correlation analysis, and other data mining. The goal of these scripts is to increase access to the wealth of structural and dynamical information that can be obtained from molecular simulations. Copyright © 2012 Wiley Periodicals, Inc.

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.

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

PubMed

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

2017-08-10

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

Alternative Solvents and Technologies for Precision Cleaning of Aerospace Components

NASA Technical Reports Server (NTRS)

Grandelli, Heather; Maloney, Phillip; DeVor, Robert; Hintze, Paul

2014-01-01

Precision cleaning solvents for aerospace components and oxygen fuel systems, including currently used Vertrel-MCA, have a negative environmental legacy, high global warming potential, and have polluted cleaning sites. Thus, alternative solvents and technologies are being investigated with the aim of achieving precision contamination levels of less than 1 mg/sq ft. The technologies being evaluated are ultrasonic bath cleaning, plasma cleaning and supercritical carbon dioxide cleaning.

Reinventing Design Principles for Developing Low-Viscosity Carbon Dioxide-Binding Organic Liquids for Flue Gas Clean Up

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

None, None

2017-01-11

Anthropogenic carbon dioxide (CO 2) emission from point sources, such as coal fired-power plants, account for the majority of the green houses gasses in the atmosphere. Capture, storage and utilization are required to mitigate adverse environmental effects. Aqueous amine-based CO 2 capture solvents are currently considered the industry standard, but deployment to market is limited by their high regeneration energy demand. In that context, energy efficient and less-viscous water-lean transformational solvent systems known as CO 2 Binding Organic Liquids (CO 2BOLs) are being developed in our group to advance this technology to commercialization. Herein, we present a logical design approachmore » based on fundamental concepts of organic chemistry and computer simulations aimed at lowering solvent viscosity. Conceptually, viscosity reduction would be achieved by systemmatic methods such as introduction of steric hindrance on the anion to minimize the intermolecular cation-anion interactions, fine tuning the electronics, hydrogen bonding orientation and strength, and charge solvation. Conventional standard trial-and-error approaches while effective, are time consuming and economically expensive. Herein, we rethink the metrics and design principles of low-viscosity CO 2 capture solvents using a combined synthesis and computational modeling approach. We critically study the impacts of modyfying factors such as as orientation of hydrogen bonding, introduction of higher degrees of freedom and cation or anion charge solvation and assess if or how each factor impacts viscosity of CO 2BOL CO 2 capture solvents. Ultimately, we found that hydrogen bond orientation and strength is predominantly influencing the viscosity in CO 2BOL solvents. With this knowledge, a new 1-MEIPADM-2-BOL CO 2BOL variant was synthesized and tested, resulting in a solvent that is approximately 60% less viscous at 25 mol% CO 2 loading with respect to our base compound 1-IPADM-2-BOL. The insights gained from the current study redefines the fundamental concepts and understanding of what influences viscosity in concentrated organic CO 2 capture solvents.« less

Considerations for spectroscopy of liquid-exfoliated 2D materials: emerging photoluminescence of N-methyl-2-pyrrolidone.

PubMed

Ogilvie, Sean P; Large, Matthew J; Fratta, Giuseppe; Meloni, Manuela; Canton-Vitoria, Ruben; Tagmatarchis, Nikos; Massuyeau, Florian; Ewels, Christopher P; King, Alice A K; Dalton, Alan B

2017-12-01

N-methyl-2-pyrrolidone (NMP) has been shown to be the most effective solvent for liquid phase exfoliation and dispersion of a range of 2D materials including graphene, molybdenum disulphide (MoS 2 ) and black phosphorus. However, NMP is also known to be susceptible to sonochemical degradation during exfoliation. We report that this degradation gives rise to strong visible photoluminescence of NMP. Sonochemical modification is shown to influence exfoliation of layered materials in NMP and the optical absorbance of the solvent in the dispersion. The emerging optical properties of the degraded solvent present challenges for spectroscopy of nanomaterial dispersions; most notably the possibility of observing solvent photoluminescence in the spectra of 2D materials such as MoS 2 , highlighting the need for stable solvents and exfoliation processes to minimise the influence of solvent degradation on the properties of liquid-exfoliated 2D materials.

Energy storage devices having anodes containing Mg and electrolytes utilized therein

DOEpatents

Shao, Yuyan; Liu, Jun

2015-08-18

For a metal anode in a battery, the capacity fade is a significant consideration. In energy storage devices having an anode that includes Mg, the cycling stability can be improved by an electrolyte having a first salt, a second salt, and an organic solvent. Examples of the organic solvent include diglyme, triglyme, tetraglyme, or a combination thereof. The first salt can have a magnesium cation and be substantially soluble in the organic solvent. The second salt can enhance the solubility of the first salt and can have a magnesium cation or a lithium cation. The first salt, the second salt, or both have a BH.sub.4 anion.

Method for molding ceramic powders using a water-based gel casting

DOEpatents

Janney, Mark A.; Omatete, Ogbemi O.

1991-07-02

A method for molding ceramic powders comprises forming a slurry mixture including ceramic powder, a dispersant, and a monomer solution. The monomer solution includes at least one monofunctional monomer and at least one difunctional monomer, a free-radical initiator, and a aqueous solvent. The slurry mixture is transferred to a mold, and the mold containing the slurry mixture is heated to polymerize and crosslink the monomer and form a firm polymer-solvent gel matrix. The solid product any be removed from the mold and heated to first remove the solvent and subsequently remove the polymer, whereafter the product may be sintered.

Method for molding ceramic powders using a water-based gel casting process

DOEpatents

Jenny, Mark A.; Omalete, Ogbemi O.

1992-09-08

A method for molding ceramic powders comprises forming a slurry mixture including ceramic powder, a dispersant, and a monomer solution. The monomer solution includes at least one monofunctional monomer and at least one difunctional monomer, a free-radical initiator, and a aqueous solvent. The slurry mixture is transferred to a mold, and the mold containing the slurry mixture is heated to polymerize and crosslink the monomer and form a firm polymer-solvent gel matrix. The solid product may be removed from the mold and heated to first remove the solvent and subsequently remove the polymer, whereafter the product may be sintered.

U. S. EPA’S APPROACH FOR CHLORINATED SOLVENTS

EPA Science Inventory

The approach for chlorinated solvents is similar to the approach for petroleum hydrocarbons. However, there are more mechanisms of removal, including reductive dechlorination (biotic or abiotic), dehydrochloroelimination (abiotic), and hydrolysis (biotic or abiotic). As a resul...

Inert Reassessment Document for Acetone - CAS No. 67-64-1

EPA Pesticide Factsheets

Acetone is a highly volatile chemical that is used as an inert ingredient, a solvent/co-solvent, in a variety of pesticide products (including outdoor yard, garden and turf products, and agricultural crop products).

Membrane augmented distillation to separate solvents from water

DOEpatents

Huang, Yu; Baker, Richard W.; Daniels, Rami; Aldajani, Tiem; Ly, Jennifer H.; Alvarez, Franklin R.; Vane, Leland M.

2012-09-11

Processes for removing water from organic solvents, such as ethanol. The processes include distillation to form a rectified overhead vapor, compression of the rectified vapor, and treatment of the compressed vapor by two sequential membrane separation steps.

Surfactant Behavior of Sodium Dodecylsulfate in Deep Eutectic Solvent Choline Chloride/Urea.

PubMed

Arnold, T; Jackson, A J; Sanchez-Fernandez, A; Magnone, D; Terry, A E; Edler, K J

2015-12-01

Deep eutectic solvents (DES) resemble ionic liquids but are formed from an ionic mixture instead of being a single ionic compound. Here we present some results that demonstrate that surfactant sodium dodecyl sulfate (SDS) remains surface-active and shows self-assembly phenomena in the most commonly studied DES, choline chloride/urea. X-ray reflectivity (XRR) and small angle neutron scattering (SANS) suggest that the behavior is significantly different from that in water. Our SANS data supports our determination of the critical micelle concentration using surface-tension measurements and suggests that the micelles formed in DES do not have the same shape and size as those seen in water. Reflectivity measurements have also demonstrated that the surfactants remain surface-active below this concentration.

Safety management of an underground-based gravitational wave telescope: KAGRA

NASA Astrophysics Data System (ADS)

Ohishi, Naoko; Miyoki, Shinji; Uchiyama, Takashi; Miyakawa, Osamu; Ohashi, Masatake

2014-08-01

KAGRA is a unique gravitational wave telescope with its location underground and use of cryogenic mirrors. Safety management plays an important role for secure development and operation of such a unique and large facility. Based on relevant law in Japan, Labor Standard Act and Industrial Safety and Health Law, various countermeasures are mandated to avoid foreseeable accidents and diseases. In addition to the usual safety management of hazardous materials, such as cranes, organic solvents, lasers, there are specific safety issues in the tunnel. Prevention of collapse, flood, and fire accidents are the most critical issues for the underground facility. Ventilation is also important for prevention of air pollution by carbon monoxide, carbon dioxide, organic solvents and radon. Oxygen deficiency should also be prevented.

Solvent Recycling for Shipyards

DTIC Science & Technology

1993-05-01

Suvey results are included in Section 5) Survey manufacturers and compile information on available equipment and features . (Data is summarized in Section...should be placed on safety features . Important safety features include explosion-proof electricals and grounding protection, overpressure relief valves...solvent can dissolve a polymer plastic liner, or extract water from a clay liner, resulting in liner leakage. The threat is compounded by the ability

A Versatile and Scalable Approach toward Robust Superhydrophobic Porous Materials with Excellent Absorbency and Flame Retardancy

NASA Astrophysics Data System (ADS)

Ruan, Changping; Shen, Mengxia; Ren, Xiaoyan; Ai, Kelong; Lu, Lehui

2016-08-01

The frequent oil spillages and the industrial discharge of organic contaminants have not only created severe environmental and ecological crises, but also cause a risk of fire and explosion. These environmental and safety issues emphasize the urgent need for materials that possess superior sorption capability and less flammability and thus can effectively and safely clean up the floating oils and water-insoluble organic compounds. Here we present the successful hydrophobic modification of the flame retardant melamine sponge with a commercial fluorosilicone, by using a facile one-step solvent-free approach and demonstrate that the resultant superhydrophobic sponge not only exhibits extraordinary absorption efficiency (including high capacity, superior selectivity, good recyclability, and simple recycling routes), but also retains excellent flame retardancy and robust stability. In comparison to conventional methods, which usually utilize massive organic solvents, the present approach does not involve any complicated process or sophisticated equipment nor generates any waste liquids, and thus is a more labor-saving, environment-friendly, energy-efficient and cost-effective strategy for the hydrophobic modification. Taking into account the critical role of hydrophobic porous materials, especially in the field of environmental remediation, the approach presented herein would be highly valuable for environmental remediation and industrial applications.

A Versatile and Scalable Approach toward Robust Superhydrophobic Porous Materials with Excellent Absorbency and Flame Retardancy

PubMed Central

Ruan, Changping; Shen, Mengxia; Ren, Xiaoyan; Ai, Kelong; Lu, Lehui

2016-01-01

The frequent oil spillages and the industrial discharge of organic contaminants have not only created severe environmental and ecological crises, but also cause a risk of fire and explosion. These environmental and safety issues emphasize the urgent need for materials that possess superior sorption capability and less flammability and thus can effectively and safely clean up the floating oils and water-insoluble organic compounds. Here we present the successful hydrophobic modification of the flame retardant melamine sponge with a commercial fluorosilicone, by using a facile one-step solvent-free approach and demonstrate that the resultant superhydrophobic sponge not only exhibits extraordinary absorption efficiency (including high capacity, superior selectivity, good recyclability, and simple recycling routes), but also retains excellent flame retardancy and robust stability. In comparison to conventional methods, which usually utilize massive organic solvents, the present approach does not involve any complicated process or sophisticated equipment nor generates any waste liquids, and thus is a more labor-saving, environment-friendly, energy-efficient and cost-effective strategy for the hydrophobic modification. Taking into account the critical role of hydrophobic porous materials, especially in the field of environmental remediation, the approach presented herein would be highly valuable for environmental remediation and industrial applications. PMID:27501762

Single-molecule spectroscopy of the unexpected collapse of an unfolded protein at low pH

NASA Astrophysics Data System (ADS)

Hofmann, Hagen; Nettels, Daniel; Schuler, Benjamin

2013-09-01

The dimensions of intrinsically disordered and unfolded proteins critically depend on the solution conditions, such as temperature, pH, ionic strength, and osmolyte or denarurant concentration. However, a quantitative understanding of how the complex combination of chain-chain and chain-solvent interactions is affected by the solvent is still missing. Here, we take a step towards this goal by investigating the combined effect of pH and denaturants on the dimensions of an unfolded protein. We use single-molecule fluorescence spectroscopy to extract the dimensions of unfolded cold shock protein (CspTm) in mixtures of the denaturants urea and guanidinium chloride (GdmCl) at neutral and acidic pH. Surprisingly, even though a change in pH from 7 to 2.9 increases the net charge of CspTm from -3.8 to +10.2, the radius of gyration of the chain is very similar under both conditions, indicating that protonation of acidic side chains at low pH results in additional hydrophobic interactions. We use a simple shared binding site model that describes the joint effect of urea and GdmCl, together with polyampholyte theory and an ion cloud model that includes the chemical free energy of counterion interactions and side chain protonation, to quantify this effect.

Application of Radiation Chemistry to Some Selected Technological Issues Related to the Development of Nuclear Energy.

PubMed

Bobrowski, Krzysztof; Skotnicki, Konrad; Szreder, Tomasz

2016-10-01

The most important contributions of radiation chemistry to some selected technological issues related to water-cooled reactors, reprocessing of spent nuclear fuel and high-level radioactive wastes, and fuel evolution during final radioactive waste disposal are highlighted. Chemical reactions occurring at the operating temperatures and pressures of reactors and involving primary transients and stable products from water radiolysis are presented and discussed in terms of the kinetic parameters and radiation chemical yields. The knowledge of these parameters is essential since they serve as input data to the models of water radiolysis in the primary loop of light water reactors and super critical water reactors. Selected features of water radiolysis in heterogeneous systems, such as aqueous nanoparticle suspensions and slurries, ceramic oxides surfaces, nanoporous, and cement-based materials, are discussed. They are of particular concern in the primary cooling loops in nuclear reactors and long-term storage of nuclear waste in geological repositories. This also includes radiation-induced processes related to corrosion of cladding materials and copper-coated iron canisters, dissolution of spent nuclear fuel, and changes of bentonite clays properties. Radiation-induced processes affecting stability of solvents and solvent extraction ligands as well oxidation states of actinide metal ions during recycling of the spent nuclear fuel are also briefly summarized.

Vibrational energy transfer between carbon nanotubes and liquid water: a molecular dynamics study.

PubMed

Nelson, Tammie R; Chaban, Vitaly V; Kalugin, Oleg N; Prezhdo, Oleg V

2010-04-08

The rates and magnitudes of vibrational energy transfer between single-wall carbon nanotubes (CNTs) and water are investigated by classical molecular dynamics. The interactions between the CNT and solvent confined inside of the tube, the CNT and solvent surrounding the tube, as well as the solvent inside and outside of the tube are considered for the (11,11), (15,15), and (19,19) armchair CNTs. The vibrational energy transfer exhibits two time scales, subpicosecond and picosecond, of roughly equal importance. Solvent molecules confined within CNTs are more strongly coupled to the tubes than the outside molecules. The energy exchange is facilitated by slow collective motions, including CNT radial breathing modes (RBM). The transfer rate between CNTs and the inside solvent shows strong dependence on the CNT diameter. In smaller tubes, the transfer is faster and the solvent coupling to RBMs is stronger. The magnitude of the CNT-outside solvent interaction scales with the CNT surface area, while that of the CNT-inside solvent exhibits scaling that is intermediate between the CNT volume and surface. The Coulomb interaction between the solvent molecules inside and outside of the CNTs is much weaker than the CNT-solvent interactions. The results indicate that the excitation energy supplied to CNTs in chemical and biological applications is rapidly deposited to the active molecular agents and should remain localized sufficiently long in order to perform the desired function.

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

Solvent dynamical control of ultrafast ground state electron transfer: implications for Class II-III mixed valency.

PubMed

Lear, Benjamin J; Glover, Starla D; Salsman, J Catherine; Londergan, Casey H; Kubiak, Clifford P

2007-10-24

We relate the solvent and temperature dependence of the rates of intramolecular electron transfer (ET) of mixed valence complexes of the type {[Ru3O(OAc)6(CO)(L)]2-BL}-1, where L = pyridyl ligand and BL = pyrazine. Complexes were reduced chemically or electrochemically to obtain the mixed valence anions in seven solvents: acetonitrile, methylene chloride, dimethylformamide, tetrahydrofuran, dimethylsulfoxide, chloroform, and hexamethylphosphoramide. Rate constants for intramolecular ET were estimated by simulating the observed degree of nu(CO) IR band shape coalescence in the mixed valence state. Correlations between rate constants for ET and solvent properties including static dielectric constant, optical dielectric constant, the quantity 1/epsilonop - 1/epsilonS, microscopic solvent polarity, viscosity, cardinal rotational moments of inertia, and solvent relaxation times were examined. In the temperature study, the complexes displayed a sharp increase in the ket as the freezing points of the solvents methylene chloride and acetonitrile were approached. The solvent phase transition causes a localized-to-delocalized transition in the mixed valence ions and an acceleration in the rate of ET. This is explained in terms of decoupling the slower solvent motions involved in the frequency factor nuN which increases the value of nuN. The observed solvent and temperature dependence of the ket for these complexes is used in order to formulate a new definition for Robin-Day class II-III mixed valence compounds. Specifically, it is proposed that class II-III compounds are those for which thermodynamic properties of the solvent exert no control over ket, but the dynamic properties of the solvent still influence ket.

Sharp Interface Tracking in Rotating Microflows of Solvent Extraction

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

Glimm, James; Almeida, Valmor de; Jiao, Xiangmin

2013-01-08

The objective of this project is to develop a specialized sharp interface tracking simulation capability for predicting interaction of micron-sized drops and bubbles in rotating flows relevant to optimized design of contactor devices used in solvent extraction processes of spent nuclear fuel reprocessing. The primary outcomes of this project include the capability to resolve drops and bubbles micro-hydrodynamics in solvent extraction contactors, determining from first principles continuum fluid mechanics how micro-drops and bubbles interact with each other and the surrounding shearing fluid for realistic flows. In the near term, this effort will play a central role in providing parameters andmore » insight into the flow dynamics of models that average over coarser scales, say at the millimeter unit length. In the longer term, it will prove to be the platform to conduct full-device, detailed simulations as parallel computing power reaches the exaflop level. The team will develop an accurate simulation tool for flows containing interacting droplets and bubbles with sharp interfaces under conditions that mimic those found in realistic contactor operations. The main objective is to create an off-line simulation capability to model drop and bubble interactions in a domain representative of the averaged length scale. The technical approach is to combine robust interface tracking software, subgrid modeling, validation quality experiments, powerful computational hardware, and a team with simulation modeling, physical modeling and technology integration experience. Simulations will then fully resolve the microflow of drops and bubbles at the microsecond time scale. This approach is computationally intensive but very accurate in treating important coupled physical phenomena in the vicinity of interfaces. The method makes it possible to resolve spatial scales smaller than the typical distance between bubbles and to model some non-equilibrium thermodynamic features such as finite critical tension in cavitating liquids« less

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

NASA Astrophysics Data System (ADS)

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

2018-01-01

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

Superfund Record of Decision (EPA Region 5): Pristine, Inc. , Reading, OH. (First remedial action), March 1990. (Amendment). Final report

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

Not Available

The 2-acre Pristine site is in Reading, Hamilton County, Ohio. The site is bordered by industrial and residential areas, including a trailer park three hundred feet northeast of the site. In 1979, State investigations identified as many as 8,000 to 10,000 drums and several thousand gallons of liquid wastes onsite. Types of waste included acids, solvents, pesticides, and PCBs. From 1980 to 1983, EPA and Pristine removed onsite wastes including paint and solvent sludge, solvents, pesticides, organics, PCB-contaminated soil, and incinerator ash. The ROD amends the soil component remedy of the 1987 ROD from in-situ vitrification to incineration and soilmore » vapor extraction. The primary contaminants of concern affecting the soil, sediment, debris, and ground water are VOCs including benzene, PCE, TCE, and xylenes; other organics including dioxin and pesticides such as DDT; metals including lead, chromium, and arsenic; and other inorganics.« less

Analysis of Eight Oil Spill Dispersants Using Rapid, In Vitro Tests for Endocrine and Other Biological Activity

EPA Science Inventory

The Deepwater Horizon oil spill has led to the use of >1 M gallons of oil spill dispersants, which are mixtures of surfactants and solvents. Because of this large scale use there is a critical need to understand the potential for toxicity of the currently used dispersant and pote...

How Efficient Is My (Medicinal) Chemistry?

PubMed Central

Vanden Eynde, Jean Jacques

2016-01-01

“Greening” a chemical transformation is not about only changing the nature of a solvent or decreasing the reaction temperature. There are metrics enabling a critical quantification of the efficiency of an experimental protocol. Some of them are applied to different sequences for the preparation of paracetamol in order to understand their performance parameters and elucidate pathways for improvement. PMID:27196914

Determination of terpenoid content in pine by organic solvent extraction and fast-GC analysis

DOE PAGES

Harman-Ware, Anne E.; Sykes, Robert; Peter, Gary F.; ...

2016-01-25

Terpenoids, naturally occurring compounds derived from isoprene units present in pine oleoresin, are a valuable source of chemicals used in solvents, fragrances, flavors, and have shown potential use as a biofuel. This paper describes a method to extract and analyze the terpenoids present in loblolly pine saplings and pine lighter wood. Various extraction solvents were tested over different times and temperatures. Samples were analyzed by pyrolysis-molecular beam mass spectrometry before and after extractions to monitor the extraction efficiency. The pyrolysis studies indicated that the optimal extraction method used a 1:1 hexane/acetone solvent system at 22°C for 1 h. Extracts frommore » the hexane/acetone experiments were analyzed using a low thermal mass modular accelerated column heater for fast-GC/FID analysis. The most abundant terpenoids from the pine samples were quantified, using standard curves, and included the monoterpenes, α- and β-pinene, camphene, and δ-carene. Sesquiterpenes analyzed included caryophyllene, humulene, and α-bisabolene. In conclusion, diterpenoid resin acids were quantified in derivatized extractions, including pimaric, isopimaric, levopimaric, palustric, dehydroabietic, abietic, and neoabietic acids.« less

MICROWAVES IN GREEN AND SUSTAINABLE CHEMISTRY

EPA Science Inventory

In this chapter, we have outlined roles of microwave chemistry in the establishment of green and sustainable chemistry. Many examples, mostly from the authors' laboratories, have been presented of green microwave processes under solvent-free conditions or with solvents, including...

MICROWAVE-FACILITATED MULTICOMPONENT REACTIONS UNDER SOLVENT-FREE CONDITIONS

EPA Science Inventory

The application of microwave-expedited solvent-free synthetic protocols in multi-component (MCC) reactions will be exemplified by several condensation and cyclization reactions including the rapid one-pot assembly of heterocyclic compounds from in situ generated intermediates. R...

Prediction of Solvent Physical Properties using the Hierarchical Clustering Method

EPA Science Inventory

Recently a QSAR (Quantitative Structure Activity Relationship) method, the hierarchical clustering method, was developed to estimate acute toxicity values for large, diverse datasets. This methodology has now been applied to the estimate solvent physical properties including sur...

Peptide chain dynamics in light and heavy water: zooming in on internal friction.

PubMed

Schulz, Julius C F; Schmidt, Lennart; Best, Robert B; Dzubiella, Joachim; Netz, Roland R

2012-04-11

Frictional effects due to the chain itself, rather than the solvent, may have a significant effect on protein dynamics. Experimentally, such "internal friction" has been investigated by studying folding or binding kinetics at varying solvent viscosity; however, the molecular origin of these effects is hard to pinpoint. We consider the kinetics of disordered glycine-serine and α-helix forming alanine peptides and a coarse-grained protein folding model in explicit-solvent molecular dynamics simulations. By varying the solvent mass over more than two orders of magnitude, we alter only the solvent viscosity and not the folding free energy. Folding dynamics at the near-vanishing solvent viscosities accessible by this approach suggests that solvent and internal friction effects are intrinsically entangled. This finding is rationalized by calculation of the polymer end-to-end distance dynamics from a Rouse model that includes internal friction. An analysis of the friction profile along different reaction coordinates, extracted from the simulation data, demonstrates that internal as well as solvent friction varies substantially along the folding pathways and furthermore suggests a connection between friction and the formation of hydrogen bonds upon folding. © 2012 American Chemical Society

Apparatus and method for reprocessing and separating spent nuclear fuels. [Patent application

DOEpatents

Krikorian, O.H.; Grens, J.Z.; Parrish, W.H. Sr.; Coops, M.S.

1982-01-19

A method and apparatus for separating and reprocessing spent nuclear fuels includes a separation vessel housing a molten metal solvent in a reaction region, a reflux region positioned above and adjacent to the reaction region, and a porous filter member defining the bottom of the separation vessel in a supporting relationship with the metal solvent. Spent fuels are added to the metal solvent. A nonoxidizing nitrogen-containing gas is introduced into the separation vessel, forming solid actinide nitrides in the metal solvent from actinide fuels, while leaving other fission products in solution. A pressure of about 1.1 to 1.2 atm is applied in the reflux region, forcing the molten metal solvent and soluble fission products out of the vessel, while leaving the solid actinide nitrides in the separation vessel.

Biofoam II

DOEpatents

Morrison, R.L.

1994-11-01

Biofoam is a rigid, microcellular organic foam made from organic materials derived from natural products and biological organisms. Starting materials include agar, agarose, gelatin, algin, alginates, gellan gum, and microcrystalline cellulose. The organic material is dissolved in a polar solvent, typically water, and the mixture is gelled. The water in the gel pores is replaced at least once with another solvent to reduce the pore size of the final biofoam. The solvent in the gel pores may be replaced several times. After the final replacement of solvent, the gel is frozen and freeze-dried to form a biofoam. Translucent biofoams are formed by selecting a final solvent that forms very small crystals. A variety of crystalline, fibrous, amorphous, or metallic additives may be incorporated into the foam structure to produce lightweight composite materials with enhanced strength and insulating properties. 1 fig.

Biofoam II

DOEpatents

Morrison, Robert L.

1994-01-01

Biofoam is a rigid, microcellular organic foam made from organic materials derived from natural products and biological organisms. Starting materials include agar, agarose, gelatin, algin, alginates, gellan gum, and microcrystalline cellulose. The organic material is dissolved in a polar solvent, typically water, and the mixture is gelled. The water in the gel pores is replaced at least once with another solvent to reduce the pore size of the final biofoam. The solvent in the gel pores may be replaced several times. After the final replacement of solvent, the gel is frozen and freeze-dried to form a biofoam. Translucent biofoams are formed by selecting a final solvent that forms very small crystals. A variety of crystalline, fibrous, amorphous, or metallic additives may be incorporated into the foam structure to produce lightweight composite materials with enhanced strength and insulating properties.

Preparation of Active Proteins, Vaccines and Pharmaceuticals as Fine Powders using Supercritical or Near-Critical Fluids

PubMed Central

Villa, Joseph A.; Huang, Edward T. S.; Yang, Tzung-Horng; Carpenter, John F.; Sievers, Robert E.

2008-01-01

Supercritical or near-critical fluid processes for generating microparticles have enjoyed considerable attention in the past decade or so, with good success for substances soluble in supercritical fluids or organic solvents. In this review, we survey their application to the production of protein particles. A recently developed process known as CO2-assisted nebulization with a Bubble Dryer® (CAN-BD) has been demonstrated to have broad applicability to small-molecule as well as macromolecule substances (including therapeutic proteins). The principles of CAN-BD are discussed as well as the stabilization, micronization and drying of a wide variety of materials. More detailed case studies are presented for three proteins, two of which are of therapeutic interest: anti-CD4 antibody (rheumatoid arthritis), α1-antitrypsin (cystic fibrosis and emphysema), and trypsinogen (a model enzyme). Dry powders were formed in which stability and activity are maintained and which are fine enough to be inhaled and reach the deep lung. Enhancement of apparent activity after CAN-BD processing was also observed in some formulation and processing conditions. PMID:18581212

Treatment System for Removing Halogenated Compounds from Contaminated Sources

NASA Technical Reports Server (NTRS)

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

2015-01-01

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

Conductivity Enhancement of PEDOT:PSS Films Through the Surface Treatment with Organic Solvent.

PubMed

Lee, Sungkoo

2016-03-01

The improvement of conductivity is a key factor in application of conducting polymer to elec- tronic devices. The conductivity enhancement of PSS films were observed after dipping in polar organic solvents, including DMSO, ethylene glycol, glycerol and IPA. The conductivity of PSS films increased from 0.5 S/cm to over 800 S/cm, that is, by a factor of more than 1,600. The conductivity enhancement was dependent on the type of organic solvents and dipping time of PSS into solvent. The enhancement of conductivity may be caused by the phase separation between PEDOT chains and PSS counter anions.

Enabling technologies and green processes in cyclodextrin chemistry

PubMed Central

Caporaso, Marina; Jicsinszky, Laszlo; Martina, Katia

2016-01-01

Summary The design of efficient synthetic green strategies for the selective modification of cyclodextrins (CDs) is still a challenging task. Outstanding results have been achieved in recent years by means of so-called enabling technologies, such as microwaves, ultrasound and ball mills, that have become irreplaceable tools in the synthesis of CD derivatives. Several examples of sonochemical selective modification of native α-, β- and γ-CDs have been reported including heterogeneous phase Pd- and Cu-catalysed hydrogenations and couplings. Microwave irradiation has emerged as the technique of choice for the production of highly substituted CD derivatives, CD grafted materials and polymers. Mechanochemical methods have successfully furnished greener, solvent-free syntheses and efficient complexation, while flow microreactors may well improve the repeatability and optimization of critical synthetic protocols. PMID:26977187

Environment and the skin

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

Suskind, R.R.

The effects of the environment on skin are surveyed. Specific patterns of adverse skin response can be characterized by morphological, physiological, and biochemical features. Cutaneous defenses and adaptations of the skin are discussed. Dermal resiliency, epidermal and pigment components, neural components, immunobiological processes, and the epidermal barrier are examined. Percutaneous absorption is reviewed. Environmental factors that cause adverse skin reactions include water, salts of heavy metals, hydrocarbons, solvents, lipids, aromatics, esters, ultraviolet light, and various modalities of ionizing radiation. Pathologic patterns and reaction sites are discussed in terms of inflammatory, allergic, benign epidermal, eccrine sweat gland, and pilosebaceous reactions, pigmentarymore » disturbances, cancer, and blood vessel changes. Although critical epidemiologic data are limited, cutaneous illnesses constitute a significant segment of occupational disease. Recommendations for further research are summarized. 42 references.« less

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.

Development of Permeable Reactive Barriers (PRB) Using Edible Oils

DTIC Science & Technology

2008-06-01

developed for the in-situ treatment of hazardous constituents including chlorinated solvents, perchlorate (ClO4-), chromate (CrO4-2) and oxidized... beef tallow, melted corn oil margarine, coconut oil and molasses supported the complete reductive dehalogenation of PCE to ethene in microcosms using...anaerobic bioremediation processes are being developed for the in-situ treatment of hazardous constituents including chlorinated solvents, perchlorate

Ultracapacitor electroyte

DOEpatents

Wei, Chang; LeBlanc, Jr., Oliver Harris; Jerabek, Elihu Calvin

2001-07-03

The invention relates to an ultracapacitor and to a method of making an ultracapacitor. The ultracapacitor of the invention includes two solid, nonporous current collectors, two porous electrodes separating the collectors, a porous separator between the electrodes and an electrolyte occupying the pores in the electrodes and separator. The electrolyte includes a cyclic carbonate solvent, a cyclic ester solvent and an electrolyte salt. The invention also relates to a stack of ultracapacitor cells.

The Effects of Organic Solvents on the Physicochemical Properties of Human Serum Albumin Nanoparticles.

PubMed

Mohammad-Beigi, Hossein; Shojaosadati, Seyed Abbas; Morshedi, Dina; Mirzazadeh, Negar; Arpanaei, Ayyoob

2016-03-01

Recently, applications of albumin nanoparticles as drug delivery carriers have increased. Most toxicology studies have shown that surface chemistry and size of nanoparticles play an important role in biocompatibility and toxicity. The effect of desolvating agents with different chemical properties on the size of synthesized HSA NPs was investigated. Acetone, ethanol, methanol, and acetonitrile were used to synthesize HSA NPs with controllable size by desolvation method. Scanning electron microscopy (SEM), dynamic light scattering (DLS), and circular dichroism (CD) were employed to characterize produced particles. Finally, the toxicity of HSA NPs synthesized under different conditions was evaluated on PC-12 cells. The sizes of synthesized particles differed according to the different solvents used. The sizes were 275.3 nm, 155.3 nm, 100.11 nm, and 66.2 nm for acetonitrile, ethanol, acetone, and methanol, respectively. CD showed that larger NPs had more changes in the secondary structures. Finally, the toxicity monitored on the cultured PC-12 cells showed no significant toxic effect through treating with these NPs at different concentrations (0-500 μg.mL -1 ). The size of HSA NPs has a strong dependency on the desolvating agent. The mechanism in which the desolvating agent affects the size of HSA NPs is complex. Various factors such as dielectric constant, polarity, functional groups, and hydrogen bonding of the solvents have the potential to affect the size and structure of HSA NPs. CD analysis suggested that the solvent denaturing capability had a critical effect on the HSA particle size. The stronger denaturing capability of the solvent resulted in the larger HSA particle size.

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.

Synthesis metal nanoparticle

DOEpatents

Bunge, Scott D.; Boyle, Timothy J.

2005-08-16

A method for providing an anhydrous route for the synthesis of amine capped coinage-metal (copper, silver, and gold) nanoparticles (NPs) using the coinage-metal mesityl (mesityl=C.sub.6 H.sub.2 (CH.sub.3).sub.3 -2,4,6) derivatives. In this method, a solution of (Cu(C.sub.6 H.sub.2 (CH.sub.3).sub.3).sub.5, (Ag(C.sub.6 H.sub.2 (CH.sub.3).sub.3).sub.4, or (Au(C.sub.6 H.sub.2 (CH.sub.3).sub.3).sub.5 is dissolved in a coordinating solvent, such as a primary, secondary, or tertiary amine; primary, secondary, or tertiary phosphine, or alkyl thiol, to produce a mesityl precursor solution. This solution is subsequently injected into an organic solvent that is heated to a temperature greater than approximately 100.degree. C. After washing with an organic solvent, such as an alcohol (including methanol, ethanol, propanol, and higher molecular-weight alcohols), oxide free coinage NP are prepared that could be extracted with a solvent, such as an aromatic solvent (including, for example, toluene, benzene, and pyridine) or an alkane (including, for example, pentane, hexane, and heptane). Characterization by UV-Vis spectroscopy and transmission electron microscopy showed that the NPs were approximately 9.2.+-.2.3 nm in size for Cu.degree., (no surface oxide present), approximately 8.5.+-.1.1 nm Ag.degree. spheres, and approximately 8-80 nm for Au.degree..

Models of globular proteins in aqueous solutions

NASA Astrophysics Data System (ADS)

Wentzel, Nathaniel James

Protein crystallization is a continuing area of research. Currently, there is no universal theory for the conditions required to crystallize proteins. A better understanding of protein crystallization will be helpful in determining protein structure and preventing and treating certain diseases. In this thesis, we will extend the understanding of globular proteins in aqueous solutions by analyzing various models for protein interactions. Experiments have shown that the liquid-liquid phase separation curves for lysozyme in solution with salt depend on salt type and salt concentration. We analyze a simple square well model for this system whose well depth depends on salt type and salt concentration, to determine the phase coexistence surfaces from experimental data. The surfaces, calculated from a single Monte Carlo simulation and a simple scaling argument, are shown as a function of temperature, salt concentration and protein concentration for two typical salts. Urate Oxidase from Asperigillus flavus is a protein used for studying the effects of polymers on the crystallization of large proteins. Experiments have determined some aspects of the phase diagram. We use Monte Carlo techniques and perturbation theory to predict the phase diagram for a model of urate oxidase in solution with PEG. The model used includes an electrostatic interaction, van der Waals attraction, and a polymerinduced depletion interaction. The results agree quantitatively with experiments. Anisotropy plays a role in globular protein interactions, including the formation of hemoglobin fibers in sickle cell disease. Also, the solvent conditions have been shown to play a strong role in the phase behavior of some aqueous protein solutions. Each has previously been treated separately in theoretical studies. Here we propose and analyze a simple, combined model that treats both anisotropy and solvent effects. We find that this model qualitatively explains some phase behavior, including the existence of a lower critical point under certain conditions.

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

DOEpatents

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

2014-06-03

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

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

DOEpatents

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

2015-09-29

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

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

DOEpatents

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

2013-08-27

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

Optical and Photophysical Investigation of (2E)-1-(2,5-Dimethylfuran-3-Yl)-3-(9-Ethyl-9H-Carbazol-3-Yl)Prop-2-en-1-One (DEPO) by Spectrofluorometer in Organized Medium.

PubMed

Asiri, Abdullah M; Al-Dies, Al-Anood M; Khan, Salman A

2017-07-01

(2E)-1-(2,5-dimethylfuran-3-yl)-3-(9-ethyl-9H-carbazol-3-yl)prop-2-en-1-one (DEPO) was prepared by the reaction of 9-ethyl-9H-carbazole-3-carbaldehyde with 1-(2,5-dimethylfuran-3-yl)ethanone under microwave irradiation. The structure of DEPO was established experimentally by EI-MS, FT-IR, 1 H and 13 C NMR spectral studies. Electronic absorption and emission spectra of DEPO were studied in different solvents on the basis of polarities, and the obtain data were used to determine the solvatochromic properties such as extinction coefficient, oscillator strength, transition dipole moment, stokes shift, fluorescence quantum yield and photochemical quantum yield. Photochemical quantum yield (Φ c ) of DEPO dye was determined in different solvent. The dye comparatively photostable in DMSO but undergoes photodecomposition in chloro methane solvents. The DEPO dye may be use as probe or quencher to determine critical micelle concentration (CMC) of cetyltri methyl ammonium bromide (CTAB) and sodium dodecyl sulfate (SDS).

Reversible Chromatic Response of Polydiacetylene Derivative Vesicles in D2O Solvent.

PubMed

Shin, Min Jae; Kim, Jong-Duk

2016-01-26

The thermal chromatic sensitivity of polydiacetylenes (PDAs) with 10,12-pentacosadiynoic acid (PCDA) derivatives, which have a hydroxyl group (HEEPCDA) and an amine group (APPCDA), were investigated using D2O and H2O as solvents. The vesicle solution with polymerized HEEPCDA exhibited a reversible chromatic response during the heating and cooling cycle in D2O, but not in H2O. On the other hand, the vesicle solution with the polymerized APPCDA exhibited a reversible chromatic response in H2O during the heating and cooling cycle, but the color of the solution did not change much in D2O. The critical vesicle concentration of HEEPCDA was lower in D2O than in H2O, and the chromatic sensitivity of the polymerized vesicles to temperature was slower in D2O than in H2O. We think that it is due to D2O being a more highly structured solvent than H2O with the hydrogen bonding in D2O stronger than that in H2O.

Compatibility of Halthane 88-3 urethane adhesive with the replacement cleaning solvent D-Limonene

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

LeMay, J.D.; Mendoza, B.

1991-08-01

D-Limonene, (R)1-methyl-4-isopropenyl-1-cyclohexene, has been identified as a leading replacement for chlorinated solvents traditionally used to clean electrical assemblies and critical components in some phases of weapons production. Unfortunately, d-limonene has a much lower vapor pressure than the chlorinated solvents if replaces (<2 torr at ambient). This makes its complete elimination from cleaned subassemblies potentially difficult, and gives rise to concerns about the compatibility of d-limonene with materials in the warhead. During the past year many WR polymers and adhesives have been surveyed for their compatibility with d-limonene. Preliminary test results obtained at Sandia (Albuquerque) and Allied-Signal (KCD) showed that Aluminum/Halthanemore » 88-3/Aluminum joints were destroyed during exposure to saturated d-limonene vapor. The cause of bond failure appeared to be d-limonene induced swelling of the Halthane polymer. This report describes recent work performed at LLNL to study the swelling behavior and bond strength degradation of Halthane 88-3 resulting from exposure to d-limonene vapor.« less

Microscopic solvent structure of subcritical and supercritical methanol from ultraviolet/visible absorption and fluorescence spectroscopies

NASA Astrophysics Data System (ADS)

Bulgarevich, Dmitry S.; Sako, Takeshi; Sugeta, Tsutomu; Otake, Katsuto; Takebayashi, Yoshihiro; Kamizawa, Chiyoshi; Uesugi, Masayuki; Kato, Masahiro

1999-09-01

Ultraviolet/visible absorption and fluorescence spectroscopies at different temperatures and pressures were applied to investigate the microscopic solvent structures of subcritical and supercritical methanol using 4-nitroanisole, ethyl-(4-dimethylamino)benzoate, Reichardt's dye, and anthracene as the probe molecules. It was found that at temperatures higher than 150 °C the long winding chains of sequentially hydrogen-bonded methanol molecules were probably broken, but the small hydrogen-bonded aggregates possibly existed in methanol even at higher temperature. It was also found that the solvation process of the anthracene molecule in the S0-ground state obeyed the Langmuir adsorption model. However, in the case of fluorescence measurements in supercritical methanol, we detected deviations from the simple Langmuir adsorption model. These deviations were explained in terms of preferential solvation of the solvent molecules around photoexcited anthracene. Judging from the experimental results, it was concluded that the local density augmentation of the supercritical methanol around the nonpolar solute was a short-ranged effect, which did not correspond directly to the large isothermal compressibility of fluid near the critical point.

Photoinduced intramolecular charge transfer and photophysical characteristics of (2Z)-3-[4-(dimethylamino) phenyl]-2-(2-methylphenyl) prop-2-ene-nitrile (DPM) in different media

NASA Astrophysics Data System (ADS)

Asiri, Abdullah M.; El-Daly, Samy A.; Alamry, Khalid A.; Arshad, Muhammad Nadeem; Pannipara, Mehboobali

2015-10-01

A new fluorophore, (2Z)-3-[4-(dimethylamino) phenyl]-2-(2-methylphenyl) prop-2-ene-nitrile (DPM), was synthesized by knoevenagel condensation of 4-(dimethylamino) benzaldehyde and 2-methylbenzyl cyanide in ethanol using NaOH as base. The electronic absorption and emission characteristic of DPM was studied in different solvents. The X-ray crystallographic structure of DPM was also investigated. A crystalline solid of DPM gives a strong green emission at about 533 nm; these phenomena are important for the application of DPM dye in organic photo emitting diode. DPM exhibits a red shift in its emission spectrum as solvent polarity increases, indicating a large change in the dipole moment of dye molecule upon excitation due to intramolecular charge transfer in excited DPM*. The fluorescence quantum yield depends strongly on the properties of the solvents, which was attributed to positive and negative solvatokinetic effects. The DPM dye displays solubilization in cationic (CTAB) micelle and could be used as a probe to determine the critical micelle concentration (CMC) of CTAB.

Cryogenic homogenization and sampling of heterogeneous multi-phase feedstock

DOEpatents

Doyle, Glenn Michael; Ideker, Virgene Linda; Siegwarth, James David

2002-01-01

An apparatus and process for producing a homogeneous analytical sample from a heterogenous feedstock by: providing the mixed feedstock, reducing the temperature of the feedstock to a temperature below a critical temperature, reducing the size of the feedstock components, blending the reduced size feedstock to form a homogeneous mixture; and obtaining a representative sample of the homogeneous mixture. The size reduction and blending steps are performed at temperatures below the critical temperature in order to retain organic compounds in the form of solvents, oils, or liquids that may be adsorbed onto or absorbed into the solid components of the mixture, while also improving the efficiency of the size reduction. Preferably, the critical temperature is less than 77 K (-196.degree. C.). Further, with the process of this invention the representative sample may be maintained below the critical temperature until being analyzed.

ZnS/Zn(O,OH)S-based buffer layer deposition for solar cells

DOEpatents

Bhattacharya, Raghu N [Littleton, CO

2009-11-03

The invention provides CBD ZnS/Zn(O,OH)S and spray deposited ZnS/Zn(O,OH)S buffer layers prepared from a solution of zinc salt, thiourea and ammonium hydroxide dissolved in a non-aqueous/aqueous solvent mixture or in 100% non-aqueous solvent. Non-aqueous solvents useful in the invention include methanol, isopropanol and triethyl-amine. One-step deposition procedures are described for CIS, CIGS and other solar cell devices.

Predicting solvation free energies and thermodynamics in polar solvents and mixtures using a solvation-layer interface condition

PubMed Central

Goossens, Spencer; Mehdizadeh Rahimi, Ali

2017-01-01

We demonstrate that with two small modifications, the popular dielectric continuum model is capable of predicting, with high accuracy, ion solvation thermodynamics (Gibbs free energies, entropies, and heat capacities) in numerous polar solvents. We are also able to predict ion solvation free energies in water–co-solvent mixtures over available concentration series. The first modification to the classical dielectric Poisson model is a perturbation of the macroscopic dielectric-flux interface condition at the solute–solvent interface: we add a nonlinear function of the local electric field, giving what we have called a solvation-layer interface condition (SLIC). The second modification is including the microscopic interface potential (static potential) in our model. We show that the resulting model exhibits high accuracy without the need for fitting solute atom radii in a state-dependent fashion. Compared to experimental results in nine water–co-solvent mixtures, SLIC predicts transfer free energies to within 2.5 kJ/mol. The co-solvents include both protic and aprotic species, as well as biologically relevant denaturants such as urea and dimethylformamide. Furthermore, our results indicate that the interface potential is essential to reproduce entropies and heat capacities. These and previous tests of the SLIC model indicate that it is a promising dielectric continuum model for accurate predictions in a wide range of conditions.

Predicting solvation free energies and thermodynamics in polar solvents and mixtures using a solvation-layer interface condition

NASA Astrophysics Data System (ADS)

Molavi Tabrizi, Amirhossein; Goossens, Spencer; Mehdizadeh Rahimi, Ali; Knepley, Matthew; Bardhan, Jaydeep P.

2017-03-01

We demonstrate that with two small modifications, the popular dielectric continuum model is capable of predicting, with high accuracy, ion solvation thermodynamics (Gibbs free energies, entropies, and heat capacities) in numerous polar solvents. We are also able to predict ion solvation free energies in water-co-solvent mixtures over available concentration series. The first modification to the classical dielectric Poisson model is a perturbation of the macroscopic dielectric-flux interface condition at the solute-solvent interface: we add a nonlinear function of the local electric field, giving what we have called a solvation-layer interface condition (SLIC). The second modification is including the microscopic interface potential (static potential) in our model. We show that the resulting model exhibits high accuracy without the need for fitting solute atom radii in a state-dependent fashion. Compared to experimental results in nine water-co-solvent mixtures, SLIC predicts transfer free energies to within 2.5 kJ/mol. The co-solvents include both protic and aprotic species, as well as biologically relevant denaturants such as urea and dimethylformamide. Furthermore, our results indicate that the interface potential is essential to reproduce entropies and heat capacities. These and previous tests of the SLIC model indicate that it is a promising dielectric continuum model for accurate predictions in a wide range of conditions.

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.

European solvent industry group generic exposure scenario risk and exposure tool

PubMed Central

Zaleski, Rosemary T; Qian, Hua; Zelenka, Michael P; George-Ares, Anita; Money, Chris

2014-01-01

The European Solvents Industry Group (ESIG) Generic Exposure Scenario (GES) Risk and Exposure Tool (EGRET) was developed to facilitate the safety evaluation of consumer uses of solvents, as required by the European Union Registration, Evaluation and Authorization of Chemicals (REACH) Regulation. This exposure-based risk assessment tool provides estimates of both exposure and risk characterization ratios for consumer uses. It builds upon the consumer portion of the European Center for Ecotoxicology and Toxicology of Chemicals (ECETOC) Targeted Risk Assessment (TRA) tool by implementing refinements described in ECETOC TR107. Technical enhancements included the use of additional data to refine scenario defaults and the ability to include additional parameters in exposure calculations. Scenarios were also added to cover all frequently encountered consumer uses of solvents. The TRA tool structure was modified to automatically determine conditions necessary for safe use. EGRET reports results using specific standard phrases in a format consistent with REACH exposure scenario guidance, in order that the outputs can be readily assimilated within safety data sheets and similar information technology systems. Evaluation of tool predictions for a range of commonly encountered consumer uses of solvents found it provides reasonable yet still conservative exposure estimates. PMID:23361440

European solvent industry group generic exposure scenario risk and exposure tool.

PubMed

Zaleski, Rosemary T; Qian, Hua; Zelenka, Michael P; George-Ares, Anita; Money, Chris

2014-01-01

The European Solvents Industry Group (ESIG) Generic Exposure Scenario (GES) Risk and Exposure Tool (EGRET) was developed to facilitate the safety evaluation of consumer uses of solvents, as required by the European Union Registration, Evaluation and Authorization of Chemicals (REACH) Regulation. This exposure-based risk assessment tool provides estimates of both exposure and risk characterization ratios for consumer uses. It builds upon the consumer portion of the European Center for Ecotoxicology and Toxicology of Chemicals (ECETOC) Targeted Risk Assessment (TRA) tool by implementing refinements described in ECETOC TR107. Technical enhancements included the use of additional data to refine scenario defaults and the ability to include additional parameters in exposure calculations. Scenarios were also added to cover all frequently encountered consumer uses of solvents. The TRA tool structure was modified to automatically determine conditions necessary for safe use. EGRET reports results using specific standard phrases in a format consistent with REACH exposure scenario guidance, in order that the outputs can be readily assimilated within safety data sheets and similar information technology systems. Evaluation of tool predictions for a range of commonly encountered consumer uses of solvents found it provides reasonable yet still conservative exposure estimates.

27 CFR 21.57 - Formula No. 30.

Code of Federal Regulations, 2013 CFR

2013-04-01

... than proprietary solvents or special industrial solvents). 051.Polishes. 052.Inks (not including meat..., fungicides, and other biocides. 430.Sterilizing and preserving solutions. 440.Industrial detergents and soaps... a raw material: 575.Drugs and medicinal chemicals. 576.Organo-silicone products. 579.Other chemicals...

27 CFR 21.57 - Formula No. 30.

Code of Federal Regulations, 2014 CFR

2014-04-01

... than proprietary solvents or special industrial solvents). 051.Polishes. 052.Inks (not including meat..., fungicides, and other biocides. 430.Sterilizing and preserving solutions. 440.Industrial detergents and soaps... a raw material: 575.Drugs and medicinal chemicals. 576.Organo-silicone products. 579.Other chemicals...

27 CFR 21.57 - Formula No. 30.

Code of Federal Regulations, 2011 CFR

2011-04-01

... than proprietary solvents or special industrial solvents). 051.Polishes. 052.Inks (not including meat..., fungicides, and other biocides. 430.Sterilizing and preserving solutions. 440.Industrial detergents and soaps... a raw material: 575.Drugs and medicinal chemicals. 576.Organo-silicone products. 579.Other chemicals...

27 CFR 21.57 - Formula No. 30.

Code of Federal Regulations, 2012 CFR

2012-04-01

... than proprietary solvents or special industrial solvents). 051.Polishes. 052.Inks (not including meat..., fungicides, and other biocides. 430.Sterilizing and preserving solutions. 440.Industrial detergents and soaps... a raw material: 575.Drugs and medicinal chemicals. 576.Organo-silicone products. 579.Other chemicals...

27 CFR 21.57 - Formula No. 30.

Code of Federal Regulations, 2010 CFR

2010-04-01

... than proprietary solvents or special industrial solvents). 051.Polishes. 052.Inks (not including meat..., fungicides, and other biocides. 430.Sterilizing and preserving solutions. 440.Industrial detergents and soaps... a raw material: 575.Drugs and medicinal chemicals. 576.Organo-silicone products. 579.Other chemicals...

A green deep eutectic solvent dispersive liquid-liquid micro-extraction (DES-DLLME) for the UHPLC-PDA determination of oxyprenylated phenylpropanoids in olive, soy, peanuts, corn, and sunflower oil.

PubMed

Ferrone, Vincenzo; Genovese, Salvatore; Carlucci, Maura; Tiecco, Matteo; Germani, Raimondo; Preziuso, Francesca; Epifano, Francesco; Carlucci, Giuseppe; Taddeo, Vito Alessandro

2018-04-15

A green dispersive liquid-liquid microextraction (DLLME) using deep eutectic solvent (DES) as the extracting solvent has been developed and applied for the simultaneous quantification of ferulic acid, umbelliferone, boropinic acid, 7-isopentenyloxycoumarin, 4'-geranyloxyferulic acid (GOFA), and auraptene in some vegetable oils using ultra high performance liquid chromatography (UHPLC) with photodiode array detection (PDA). All parameters in the extraction step, including selection and loading of both extracting and dispersing solvents, amount of both extractant and disperser solvent were investigated and optimized. PhAA/TMG DES achieved higher recovery and enrichment factor compared to other DESs. The validated method showed good linearity with correlation coefficients, r 2 >0.9990 for all the analytes. Furthermore, this is the first time that eco-friendly solvents are used for the extraction of oxyprenylated phenylpropanoids and the corresponding extract analyzed with ultra high performance liquid chromatography with photodiode array detection. Copyright © 2017 Elsevier Ltd. All rights reserved.

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

PubMed

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

2013-02-07

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

Phase-Change Aminopyridines as Carbon Dioxide Capture Solvents

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

Malhotra, Deepika; Page, Jordan P.; Bowden, Mark E.

Carbon dioxide is the main atmospheric greenhouse gas released from industrial point sources. In order to mitigate adverse environmental effects of these emissions, carbon capture, storage and utilization is required. To this end, several CO2 capture technologies are being developed for application in carbon capture, which include aqueous amines and water-lean solvents. Herein we report new aminopyridine solvents with the potential for CO2 capture from coal-fired power plants. These four solvents 2-picolylamine, 3-picolylamine, 4-picolylamine and N’-(pyridin-4-ylmethyl)ethane-1,2-diamine are liquids that rapidly bind CO2 to form crystalline solids at standard room temperature and pressure. These solvents have displayed high CO2 capture capacitymore » (11 - 20 wt%) and can be regenerated at temperatures in the range of 120 - 150 C. The advantage of these primary aminopyridine solvents is that crystalline salt product can be separated, making it possible to regenerate only the CO2-rich solid ultimately resulting in reduced energy penalty.« less

Quantifying Volatile Organic Compound Emissions from Solvents and their Impacts on Urban Air Quality

NASA Astrophysics Data System (ADS)

Mcdonald, B. C.; De Gouw, J. A.; Gilman, J.; Ahmadov, R.; Cappa, C. D.; Frost, G. J.; Goldstein, A. H.; Jathar, S.; Jimenez, J. L.; Kim, S. W.; McKeen, S. A.; Roberts, J. M.; Trainer, M.

2016-12-01

Solvents, which consist of personal care products, paints, degreasing agents, and other chemical products, are an important anthropogenic source of volatile organic compound (VOC) emissions. Yet there are many unresolved questions related to their emission rates, chemical composition, and relative importance on urban air quality problems. Using atmospheric measurements of speciated VOCs collected at a ground site located in the Los Angeles basin during the California Nexus (CalNex) Study in 2010, and utilizing data on the composition of solvent emissions from the California Air Resources Board (CARB), we are able to reconcile solvent emissions with ambient observations. Our analysis indicates that solvent emissions are underestimated by a factor of 2-3 in the CARB inventory. We then estimate the reactivity of solvent emissions with the hydroxyl (OH) radical, and also estimate the propensity of solvent emissions to form secondary organic aerosol (SOA). Solvents contain significant fractions of oxygenated compounds, including intermediate volatility compounds, which if released to the atmosphere are potentially reactive and can lead to the formation of SOA. Overall, our results suggest that in the Los Angeles basin, solvents are now the largest anthropogenic source of VOC emissions, OH reactivity, and SOA formation, and larger than the contribution from motor vehicles. This suggests that more research is needed in better constraining this potentially important source of urban VOC emissions.

Novel PLA-Based Conductive Polymer Composites for Biomedical Applications

NASA Astrophysics Data System (ADS)

Shah, Aziurah Mohd; Kadir, Mohammed Rafiq Abdul; Razak, Saiful Izwan Abd

2017-12-01

In this study, the electrical conductivity of polylactic acid (PLA)-based composites has been improved using polyaniline (PANI) with two different solvents: dodecylbenzene sulfonic acid and citric acid. The effects of various factors including PLA quantity, solvent concentration, type of solvent and thickness on the resistivity were investigated using the design of experiments. The experimental plan was based on irregular fraction design to develop the regression models. The results revealed that the proposed mathematical models were sufficient and could describe the performance of resistivity of PLA within the limits of a factor. The findings also indicated that thickness had the most significant effect on the resistivity of PLA, while the effect of the type of solvent was of least significance. Moreover, it was illustrated that, by incorporating two different solvents into PANI, the resistivity could be changed for further applications.

A comparison of certain extracting agents for extraction of adenosine triphosphate (ATP) from microorganisms for use in the firefly luciferase ATP assay

NASA Technical Reports Server (NTRS)

Knust, E. A.; Chappelle, E. W.; Picciolo, G. L.

1975-01-01

Firefly luciferase ATP assay is used in clinical and industrial applications, such as determination of urinary infection levels, microbial susceptibility testing, and monitoring of yeast levels in beverages. Three categories of extractants were investigated for their extracting efficiency. They were ionizing organic solvents, nonionizing organic solvents, and inorganic acids. Dimethylsulfoxide and formamide represented the ionizing organic solvents, while n-butanol, chloroform, ethanol, acetone, and methylene chloride were used for the nonionizing organic solvents. Nitric acid and perchloric acid were chosen for the inorganic acids category. Pathogens were tested with each solvent. They included: Saccharomyces carlsbergensis, E. coli, Staphylococcus aureus, Klebsiella pneumoniae, Enterobacter species, Proteus mirabilis, Proteus vulgaris, Staphylococcus epidermidis, Streptococcus faecalis, Pseudomonas aeruginosa, and Candida albicans. These results are shown in graphic representations.

Prevention of deleterious deposits in a coal liquefaction system

DOEpatents

Carr, Norman L.; Prudich, Michael E.; King, Jr., William E.; Moon, William G.

1984-07-03

A process for preventing the formation of deleterious coke deposits on the walls of coal liquefaction reactor vessels involves passing hydrogen and a feed slurry comprising feed coal and recycle liquid solvent to a coal liquefaction reaction zone while imparting a critical mixing energy of at least 3500 ergs per cubic centimeter of reaction zone volume per second to the reacting slurry.

Natural product studies of U.S. endangered plants: Volatile components of Lindera melissifolia (Lauraceae) repel mosquitoes and ticks

Treesearch

Joonseok Oh; John J. Bowling; John F. Carroll; Betul Demirci; K. Hüsnü Can Baser; Theodor D. Leininger; Ulrich R. Berniere; Mark T. Hamann

2012-01-01

The number of endangered plant species in the U.S. is significant, yet studies aimed towards utilizing these plants are limited. Ticks and mosquitoes are vectors of significant pathogenic diseases of humans. Repellents are critical means of personal protection against biting arthropods and disease transmission. The essential oil and solvent extracts from ...

Buckling Instabilities in Polymer Brush Surfaces via Postpolymerization Modification

DOE PAGES

Guo, Wei; Reese, Cassandra M.; Xiong, Li; ...

2017-10-30

We report a simple route to engineer ultrathin polymer brush surfaces with wrinkled morphologies using postpolymerization modification (PPM), where the length scale of the buckled features can be tuned using PPM reaction time. Here, we show that partial crosslinking of the outer layer of the polymer brush under poor solvent conditions is critical to obtain wrinkled morphologies upon swelling.

The Aldol Addition and Condensation: The Effect of Conditions on Reaction Pathway

ERIC Educational Resources Information Center

Crouch, R. David; Richardson, Amie; Howard, Jessica L.; Harker, Rebecca L.; Barker, Kathryn H.

2007-01-01

The reaction of a ketone and an aldehyde in aqueous Na[subscript 2]CO[subscript 2] is described. This experiment is performed in the absence of strong bases or organic solvents and offers the opportunity for students to observe the critical role that reaction temperature and base strength have in determining the product of the base-mediated…

Coal Liquefaction desulfurization process

DOEpatents

Givens, Edwin N.

1983-01-01

In a solvent refined coal liquefaction process, more effective desulfurization of the high boiling point components is effected by first stripping the solvent-coal reacted slurry of lower boiling point components, particularly including hydrogen sulfide and low molecular weight sulfur compounds, and then reacting the slurry with a solid sulfur getter material, such as iron. The sulfur getter compound, with reacted sulfur included, is then removed with other solids in the slurry.

Water solubility enhancements of DDT and trichlorobenzene by some surfactants below and above the critical micelle concentration

USGS Publications Warehouse

Kile, D.E.; Chiou, C.T.

1989-01-01

Water solubility enhancements of 1,1-bis(p-chlorophenyl)-2,2,2-trichloroethane (DDT) and 1,2,3-trichlorobenzene (TCB) by aqueous surfactants below and above their critical micelle concentrations (CMCs) have been studied at room temperature with the following surfactants: Triton X-100, Triton X-114, Triton X-405, Brij 35, sodium dodecyl sulfate, and cetyltrimethylammonium bromide. While the solubilities of DDT and TCB are greatly enhanced by all surfactants above the measured CMC, DDT also exhibits significant solubility enhancements below the CMC of the molecularly nonhomogeneous surfactants (the Triton series and Brij 35). The plot of the apparent DDT solubility against the concentration of Triton and Brij surfactants shows an uprising curve below the nominal CMC, which is attributed to the successive micellization of the heterogeneous monomer species. Above the CMC, the enhancement effect with the nonionic surfactants is closely proportional to the nonpolar chain content of the surfactant, whereas the effect with the ionic surfactants is less accountable in terms of their nonpolar chain contents. The solubilization power of a micelle relative to a bulk solvent is evaluated by a comparison of the observed micelle-water and solvent-water partition coefficients.

Anomalous viscosity effect in the early stages of the ion-assisted adhesion/fusion event between lipid bilayers: A theoretical and computational study

NASA Astrophysics Data System (ADS)

Raudino, Antonio; Marrink, Siewert J.; Pannuzzo, Martina

2013-06-01

The effect of viscosity on the encounter rate of two interacting membranes was investigated by combining a non-equilibrium Fokker-Planck model together with extensive Molecular Dynamics (MD) calculations. The encounter probability and stabilization of transient contact points represent the preliminary steps toward short-range adhesion and fusion of lipid leaflets. To strengthen our analytical model, we used a Coarse Grained MD method to follow the behavior of two charged palmitoyl oleoyl phosphatidylglycerol membranes embedded in a electrolyte-containing box at different viscosity regimes. Solvent friction was modulated by varying the concentration of a neutral, water-soluble polymer, polyethylene glycol, while contact points were stabilized by divalent ions that form bridges among juxtaposed membranes. While a naïve picture foresees a monotonous decrease of the membranes encounter rate with solvent viscosity, both the analytical model and MD simulations show a complex behavior. Under particular conditions, the encounter rate could exhibit a maximum at a critical viscosity value or for a critical concentration of bridging ions. These results seem to be confirmed by experimental observations taken from the literature.

Intestinal Water Absorption Varies with Expected Dietary Water Load among Bats but Does Not Drive Paracellular Nutrient Absorption.

PubMed

Price, Edwin R; Brun, Antonio; Gontero-Fourcade, Manuel; Fernández-Marinone, Guido; Cruz-Neto, Ariovaldo P; Karasov, William H; Caviedes-Vidal, Enrique

2015-01-01

Rapid absorption and elimination of dietary water should be particularly important to flying species and were predicted to vary with the water content of the natural diet. Additionally, high water absorption capacity was predicted to be associated with high paracellular nutrient absorption due to solvent drag. We compared the water absorption rates of sanguivorous, nectarivorous, frugivorous, and insectivorous bats in intestinal luminal perfusions. High water absorption rates were associated with high expected dietary water load but were not highly correlated with previously measured rates of (paracellular) arabinose clearance. In conjunction with these tests, we measured water absorption and the paracellular absorption of nutrients in the intestine and stomach of vampire bats using luminal perfusions to test the hypothesis that the unique elongated vampire stomach is a critical site of water absorption. Vampire bats' gastric water absorption was high compared to mice but not compared to their intestines. We therefore conclude that (1) dietary water content has influenced the evolution of intestinal water absorption capacity in bats, (2) solvent drag is not the only driver of paracellular nutrient absorption, and (3) the vampire stomach is a capable but not critical location for water absorption.

Facile synthesis of hierarchical dendritic PtPd nanogarlands supported on reduced graphene oxide with enhanced electrocatalytic properties

NASA Astrophysics Data System (ADS)

Li, Shan-Shan; Zheng, Jie-Ning; Ma, Xiaohong; Hu, Yuan-Yuan; Wang, Ai-Jun; Chen, Jian-Rong; Feng, Jiu-Ju

2014-05-01

A simple and facile method is developed for one-pot preparation of hierarchical dendritic PtPd nanogarlands supported on reduced graphene oxide (PtPd/RGO) at room temperature, without using any seed, organic solvent, or complex apparatus. It is found that octylphenoxypolyethoxyethanol (NP-40) as a soft template and its amount are critical to the formation of PtPd garlands. The as-prepared nanocomposites are further applied to methanol and ethanol oxidation with significantly enhanced electrocatalytic activity and better stability in alkaline media.A simple and facile method is developed for one-pot preparation of hierarchical dendritic PtPd nanogarlands supported on reduced graphene oxide (PtPd/RGO) at room temperature, without using any seed, organic solvent, or complex apparatus. It is found that octylphenoxypolyethoxyethanol (NP-40) as a soft template and its amount are critical to the formation of PtPd garlands. The as-prepared nanocomposites are further applied to methanol and ethanol oxidation with significantly enhanced electrocatalytic activity and better stability in alkaline media. Electronic supplementary information (ESI) available: Experimental section, Fig. S1-S12 and Tables S1 and S2. See DOI: 10.1039/c3nr06808k

Robustness of solvent/detergent treatment of plasma derivatives: a data collection from Plasma Protein Therapeutics Association member companies.

PubMed

Dichtelmüller, Herbert O; Biesert, Lothar; Fabbrizzi, Fabrizio; Gajardo, Rodrigo; Gröner, Albrecht; von Hoegen, Ilka; Jorquera, Juan I; Kempf, Christoph; Kreil, Thomas R; Pifat, Dominique; Osheroff, Wendy; Poelsler, Gerhard

2009-09-01

Solvent/detergent (S/D) treatment is an established virus inactivation technology that has been applied in the manufacture of medicinal products derived from human plasma for more than 20 years. Data on the inactivation of enveloped viruses by S/D treatment collected from seven Plasma Protein Therapeutics Association member companies demonstrate the robustness, reliability, and efficacy of this virus inactivation method. The results from 308 studies reflecting production conditions as well as technical variables significantly beyond the product release specification were evaluated for virus inactivation, comprising different combinations of solvent and detergent (tri(n-butyl) phosphate [TNBP]/Tween 80, TNBP/Triton X-100, TNBP/Na-cholate) and different products (Factor [F]VIII, F IX, and intravenous and intramuscular immunoglobulins). Neither product class, process temperature, protein concentration, nor pH value has a significant impact on virus inactivation. A variable that did appear to be critical was the concentration of solvent and detergent. The data presented here demonstrate the robustness of virus inactivation by S/D treatment for a broad spectrum of enveloped test viruses and process variables. Our data substantiate the fact that no transmission of viruses such as human immunodeficiency virus, hepatitis B virus, hepatitis C virus, or of other enveloped viruses was reported for licensed plasma derivatives since the introduction of S/D treatment.

A low viscosity, low boiling point, clean solvent system for the rapid crystallisation of highly specular perovskite films

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

Noel, Nakita K.; Habisreutinger, Severin N.; Wenger, Bernard

2017-01-01

Perovskite-based photovoltaics have, in recent years, become poised to revolutionise the solar industry. While there have been many approaches taken to the deposition of this material, one-step spin-coating remains the simplest and most widely used method in research laboratories. Although spin-coating is not recognised as the ideal manufacturing methodology, it represents a starting point from which more scalable deposition methods, such as slot-dye coating or ink-jet printing can be developed. Here, we introduce a new, low-boiling point, low viscosity solvent system that enables rapid, room temperature crystallisation of methylammonium lead triiodide perovskite films, without the use of strongly coordinating aproticmore » solvents. Through the use of this solvent, we produce dense, pinhole free films with uniform coverage, high specularity, and enhanced optoelectronic properties. We fabricate devices and achieve stabilised power conversion efficiencies of over 18% for films which have been annealed at 100 degrees C, and over 17% for films which have been dried under vacuum and have undergone no thermal processing. This deposition technique allows uniform coating on substrate areas of up to 125 cm2, showing tremendous promise for the fabrication of large area, high efficiency, solution processed devices, and represents a critical step towards industrial upscaling and large area printing of perovskite solar cells.« less

Mechanistic Study of Electrolyte Additives to Stabilize High-Voltage Cathode–Electrolyte Interface in Lithium-Ion Batteries

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

Gao, Han; Maglia, Filippo; Lamp, Peter

Current developments of electrolyte additives to stabilize electrode-electrolyte interface in Li-ion batteries highly rely on a trial-and-error search, which involves repetitive testing and intensive amount of resources. The lack of understandings on the fundamental protection mechanisms of the additives significantly increases the difficulty for the transformational development of new additives. In this study, we investigated two types of individual protection routes to build a robust cathode-electrolyte interphase at high potentials: (i) a direct reduction in the catalytic decomposition of the electrolyte solvent; and (ii) formation of a “corrosion inhibitor film” that prevents severely attack and passivation from protons that generatedmore » from the solvent oxidation, even the decomposition of solvent cannot not mitigated. Effect of three exemplary electrolyte additives: (i) lithium difluoro(oxalato)borate (LiDFOB); (ii) 3-hexylthiophene (3HT); and (iii) tris(hexafluoro-iso-propyl)phosphate (HFiP), on LiNi0.6Mn0.2Co0.2O2 (NMC 622) cathode were investigated to validate our hypothesis. It is demonstrated that understandings of both electrolyte additives and solvent are essential and careful balance between the cathode protection mechanism of additives and their side effects is critical to obtain optimum results. More importantly, this study opens up new directions of rational design of functional electrolyte additives for the next generation high-energy density lithium-ion chemistries.« less

Folding of the four-helix bundle FF domain from a compact on-pathway intermediate state is governed predominantly by water motion.

PubMed

Sekhar, Ashok; Vallurupalli, Pramodh; Kay, Lewis E

2012-11-20

Friction plays a critical role in protein folding. Frictional forces originating from random solvent and protein fluctuations both retard motion along the folding pathway and activate protein molecules to cross free energy barriers. Studies of friction thus may provide insights into the driving forces underlying protein conformational dynamics. However, the molecular origin of friction in protein folding remains poorly understood because, with the exception of the native conformer, there generally is little detailed structural information on the other states participating in the folding process. Here, we study the folding of the four-helix bundle FF domain that proceeds via a transiently formed, sparsely populated compact on-pathway folding intermediate whose structure was elucidated previously. Because the intermediate is stabilized by both native and nonnative interactions, friction in the folding transition between intermediate and folded states is expected to arise from intrachain reorganization in the protein. However, the viscosity dependencies of rates of folding from or unfolding to the intermediate, as established by relaxation dispersion NMR spectroscopy, clearly indicate that contributions from internal friction are small relative to those from solvent, so solvent frictional forces drive the folding process. Our results emphasize the importance of solvent dynamics in mediating the interconversion between protein configurations, even those that are highly compact, and in equilibrium folding/unfolding fluctuations in general.

The Influence of Carbon-Carbon Multiple Bonds on the Solvolyses of Tertiary Alkyl Halides: a Grunwald-Winstein Analysis

PubMed Central

Reis, Marina C.; Elvas-Leitão, Ruben; Martins, Filomena

2008-01-01

The influence of carbon-carbon multiple bonds on the solvolyses of 3-chloro-3-methylbutyne (1), 2-chloro-2-phenylpropane (2), 2-bromo-2-methyl-1-phenylpropane (3), 4-chloro-4-methyl-2-pentyne (4) and 2-chloro-2-methylbutane (5) is critically evaluated through the extended Grunwald-Winstein equation. Substrates 1, 3 and 5 lead to correlations with unexpected negative sensitivity, h, to changes in the aromatic ring parameter, I. It is claimed that I is not a pure parameter, reflecting also some solvent nucleophilicity, NOTs, character. In substrates 2 and 4 the possibility of rearside solvation is reduced due to steric hindrance and/or cation stabilization and the best found correlations involve only the solvent ionizing power, Y, and I. PMID:19325827

Method for producing high surface area chromia materials for catalysis

DOEpatents

Gash, Alexander E [Brentwood, CA; Satcher, Joe [Patterson, CA; Tillotson, Thomas [Tracy, CA; Hrubesh, Lawrence [Pleasanton, CA; Simpson, Randall [Livermore, CA

2007-05-01

Nanostructured chromium(III)-oxide-based materials using sol-gel processing and a synthetic route for producing such materials are disclosed herein. Monolithic aerogels and xerogels having surface areas between 150 m.sup.2/g and 520 m.sup.2/g have been produced. The synthetic method employs the use of stable and inexpensive hydrated-chromium(III) inorganic salts and common solvents such as water, ethanol, methanol, 1-propanol, t-butanol, 2-ethoxy ethanol, and ethylene glycol, DMSO, and dimethyl formamide. The synthesis involves the dissolution of the metal salt in a solvent followed by an addition of a proton scavenger, such as an epoxide, which induces gel formation in a timely manner. Both critical point (supercritical extraction) and atmospheric (low temperature evaporation) drying may be employed to produce monolithic aerogels and xerogels, respectively.

Thermal behavior of glassy phase stabilized ammonium nitrate (PSAN) thin films

DOE PAGES

Yeager, J. D.; Chellappa, R.; Singh, S.; ...

2015-06-01

Ammonium nitrate (AN) is a high interest material because of its wide usage in propellants and explosives but can be difficult to handle from a formulation standpoint. It is soluble in many common solvents and has complex phase behavior. Here, we formulate phase stabilized AN (PSAN) films in a polymer matrix and characterize thermal and phase behavior using neutron reflectometry and ellipsometry. Our PSAN films are generally stable up to 160 °C, though we observe small material loss between 60 and 100 °C, which we attribute to solvent interactions with the PSAN. Crystallization of AN from supersaturated polymer is mostmore » common at thicker regions of the film, suggesting a critical nucleation thickness for the AN which can be avoided by making very thin films.« less

[The effect of hydrophobic surface properties of protein on its resistance to denaturation by organic solvents (using modified alpha-chymotrypsin as an example].

PubMed

Kudriashova, E V; Belova, A B; Vinogradov, A A; Mozhaev, V V

1994-03-01

Catalytic activity of covalently modified alpha-chymotrypsin in water/cosolvent solutions was investigated. The stability of chymotrypsin increases upon modification with hydrophilic reagents, such as glyceraldehyde, pyrometallic and succinic anhydrides, and glucosamine. Correlation was observed between the protein's stability in organic solvents and the degree of hydrophilization of the protein's surface. The protein is the more stable, the higher are the modification degree and the hydrophilicity of the modifying residue. At a certain critical hydrophilization degree of chymotrypsin a limit of stability is achieved. The stabilization effect can be accounted for by the fact that the interaction between water molecules on the surface and protein's functional groups become stronger in the hydrophilized protein.

Effects of solvent evaporation conditions on solvent vapor annealed cylinder-forming block polymer thin films

NASA Astrophysics Data System (ADS)

Grant, Meagan; Jakubowski, William; Nelson, Gunnar; Drapes, Chloe; Baruth, A.

Solvent vapor annealing is a less time and energy intensive method compared to thermal annealing, to direct the self-assembly of block polymer thin films. Periodic nanostructures have applications in ultrafiltration, magnetic arrays, or other structures with nanometer dimensions, driving its continued interest. Our goal is to create thin films with hexagonally packed, perpendicular aligned cylinders of poly(lactide) in a poly(styrene) matrix that span the thickness of the film with low anneal times and low defect densities, all with high reproducibility, where the latter is paramount. Through the use of our computer-controlled, pneumatically-actuated, purpose-built solvent vapor annealing chamber, we have the ability to monitor and control vapor pressure, solvent concentration within the film, and solvent evaporation rate with unprecedented precision and reliability. Focusing on evaporation, we report on two previously unexplored areas, chamber pressure during solvent evaporation and the flow rate of purging gas aiding the evaporation. We will report our exhaustive results following atomic force microscopy analysis of films exposed to a wide range of pressures and flow rates. Reliably achieving well-ordered films, while occurring within a large section of this parameter space, was correlated with high-flow evaporation rates and low chamber pressures. These results have significant implications on other methods of solvent annealing, including ``jar'' techniques.

Green analytical chemistry - the use of surfactants as a replacement of organic solvents in spectroscopy

NASA Astrophysics Data System (ADS)

Pharr, Daniel Y.

2017-07-01

This chapter gives an introduction to the many practical uses of surfactants in analytical chemistry in replacing organic solvents to achieve greener chemistry. Taking a holistic approach, it covers some background of surfactants as chemical solvents, their properties and as green chemicals, including their environmental effects. The achievements of green analytical chemistry with micellar systems are reviewed in all the major areas of analytical chemistry where these reagents have been found to be useful.

Literature survey of properties of synfuels derived from coal

NASA Technical Reports Server (NTRS)

Reynolds, T. W.; Niedzwiecki, R. W.; Clark, J. S.

1980-01-01

A literature survey of the properties of synfuels for ground-based gas turbine applications is presented. Four major concepts for converting coal into liquid fuels are described: solvent extraction, catalytic liquefaction, pyrolysis, and indirect liquefaction. Data on full range syncrudes, various distillate cuts, and upgraded products are presented for fuels derived from various processes, including H-coal, synthoil, solvent-refined coal, donor solvent, zinc chloride hydrocracking, co-steam, and flash pyrolysis. Some typical ranges of data for coal-derived low Btu gases are also presented.

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

EPA Science Inventory

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

IRIS TOXICOLOGICAL REVIEW AND SUMMARY DOCUMENTS FOR 1,4 - DIOXANE

EPA Science Inventory

1,4 -Dioxane is a cyclic ether that is primarily utilized for industrial applications. These applications include 1,4 -dioxane as a solvent, reaction medium, wetting, degreasing, and dispersing agent, and for stabilization of chlorinated solvents (e.g. 1,1,1 -trichloroethane). ...

SOLVENT-BASED TO WATERBASED ADHESIVE-COATED SUBSTRATE RETROFIT - VOLUME III: LABEL MANUFACTURING CASE STUDY: NASHUA CORPORATION

EPA Science Inventory

This volume discusses Nashua Corporation's Omaha facility, a label and label stock manufacturing facility that no longer uses solvent-based adhesives. Information obtained includes issues related to the technical, economic, and environmental barriers and opportunities associated ...

Solvent-Free Synthesis of Zeolites: Mechanism and Utility.

PubMed

Wu, Qinming; Meng, Xiangju; Gao, Xionghou; Xiao, Feng-Shou

2018-05-08

Zeolites have been extensively studied for years in different areas of chemical industry, such as shape selective catalysis, ion-exchange, and gas adsorption and separation. Generally, zeolites are prepared from solvothermal synthesis in the presence of a large amounts of solvents such as water and alcohols in sealed autoclaves under autogenous pressure. Water has been regarded as essential to synthesize zeolites for fast mass transfer of reactants, but it occupies a large space in autoclaves, which greatly reduces the yield of zeolite products. Furthermore, polluted wastes and relatively high pressure due to the presence of water solvent in the synthesis also leads to environmental and safety issues. Recently, inspired by great benefits of solvent-free synthesis, including the environmental concerns, energy consumption, safety, and economic cost, researchers continually challenge the rationale of the solvent and reconsider the age-old question "Do we actually need solvents at all in zeolite synthesis?" In this Account, we briefly summarize our efforts to rationally synthesize zeolites via a solvent-free route. Our research demonstrates that a series of silica, aluminosilicate, and aluminophosphate-based zeolites can be successfully prepared by mixing, grinding, and heating starting solid materials under solvent-free conditions. Combining an organotemplate-free synthesis with a solvent-free approach maximizes the advantages resulting in a more sustainable synthetic route, which avoids using toxic and costly organic templates and the formation of harmful gases by calcination of organic templates at high temperature. Furthermore, new insights into the solvent-free crystallization process of zeolites have been provided by modern techniques such as NMR and UV-Raman spectroscopy, which should be helpful in designing new zeolite structures and developing novel routes for synthesis of zeolites. The role of water and the vital intermediates during the crystallization of zeolites have been proposed and verified. In addition to a significant reduction in liquid wastes and a remarkable increase in zeolite yields, the solvent-free synthesis of zeolites exhibits more unprecedented benefits, including (i) the formation of hierarchical micro-, meso-, and macrostructures, which benefit the mass transfer in the reactions, (ii) rapid synthesis at higher temperatures, which greatly improve the space-time yields of zeolites, and (iii) construction of a novel catalytic system for encapsulation of metal nanoparticles and metal oxide particles within zeolite crystals synergistically combining the advantages of catalytic metal nanoparticles and metal oxide particles (high activity) and zeolites (shape selectivity). We believe that the concept of "solvent-free synthesis of zeolites" would open a door for deep understanding of zeolite crystallization and the design of efficient zeolitic catalysts.

Field-portable supercritical CO{sub 2} extractor

DOEpatents

Wright, B.W.; Zemanian, T.S.; Robins, W.H.; Woodcock, L.J.

1997-06-10

The present invention is an apparatus for extracting organic compounds from solid materials. A generator vessel has a removable closure for receiving a solid or liquid solvent which is heated with a resistive heating element to a gaseous or supercritical phase. The removable closure is unencumbered because the side wall is penetrated with an outlet for the gaseous or supercritical solvent. The generator vessel further has a pressure transducer that provides an electronic signal related to pressure of the gaseous or supercritical solvent. The apparatus of the present invention further includes at least one extraction cell having a top and a bottom and a wall extending there between, wherein the bottom is sealably penetrated by an inlet for gaseous or supercritical solvent received through a manifold connected to the outlet, the top having an easy-open removable closure cap, and the wall having an outlet port. Finally, a permeable sample cartridge is included for holding the solid materials and to provide radial-flow of the extraction fluid, which is placed within the extraction cell. 10 figs.

Field-portable supercritical CO.sub.2 extractor

DOEpatents

Wright, Bob W.; Zemanian, Thomas S.; Robins, William H.; Woodcock, Leslie J.

1997-01-01

The present invention is an apparatus for extracting organic compounds from solid materials. A generator vessel has a removable closure for receiving a solid or liquid solvent which is heated with a resistive heating element to a gaseous or supercritical phase. The removable closure is unencumbered because the side wall is penetrated with an outlet for the gaseous or supercritical solvent. The generator vessel further has a pressure transducer that provides an electronic signal related to pressure of the gaseous or supercritical solvent. The apparatus of the present invention further includes at least one extraction cell having a top and a bottom and a wall extending therebetween, wherein the bottom is sealably penetrated by an inlet for gaseous or supercritical solvent received through a manifold connected to the outlet, the top having an easy-open removable closure cap, and the wall having an outlet port. Finally, a permeable sample cartridge is included for holding the solid materials and to provide radial-flow of the extraction fluid, which is placed within the extraction cell.

Dynamical studies of confined fluids and polymers

NASA Astrophysics Data System (ADS)

Grabowski, Christopher A.

Soft matter, a class of materials including polymers, colloids, and surfactant molecules, are ubiquitous in our everyday lives. Plastics, soaps, foods and living organisms are mostly comprised of soft materials. Research conducted to understand soft matter behavior at the molecular level is essential to create new materials with unique properties. Self-healing plastics, targeted drug delivery, and nanowire assemblies have all been further advanced by soft matter research. The author of this dissertation investigates fundamental soft matter systems, including polymer solutions and melts, colloid dispersions in polymer melts, and interfacial fluids. The dynamics of polymers and confined fluids were studied using the single-molecule sensitive technique of fluorescence correlation spectroscopy (FCS). Here, fluorescent dyes are attached to polymer coils or by introducing free dyes directly into the solution/film. Complementary experiments were also performed, utilizing atomic force microscopy (AFM) and ellipsometry. FCS and AFM experiments demonstrated the significant difference in properties of thin fluid films of the nearly spherical, nonpolar molecule TEHOS (tetrakis(2-ethylhexoxy)silane) when compared to its bulk counterpart. AFM experiments confirmed TEHOS orders in layers near a solid substrate. FCS experiments show that free dyes introduced in these thin films do not have a single diffusion coefficient, indicating that these films have heterogeneity at the molecular level. FCS experiments have been applied to study the diffusion of gold colloids. The diffusion of gold colloids in polymer melts was found to dramatically depart from the Stokes-Einstein prediction when colloid size was smaller than the surrounding polymer mesh size. This effect is explained by noting the viscosity experienced by the colloid is not equivalent to the overall bulk viscosity of the polymer melt. The conformational change of polymers immersed in a binary solvent was measured via FCS. This experiment was conducted to test a theory proposed by Brochard and de Gennes, who postulated a polymer chain undergoes a collapse and a dramatic re-swelling as the critical point of the binary mixture is approached. Measuring polymer chain diffusion as a function of temperature, this theory was confirmed. To my knowledge, this was the first experimental evidence of contraction/re-swelling for polymers in critical binary solvents.

Improved predictive model for n-decane kinetics across species, as a component of hydrocarbon mixtures.

PubMed

Merrill, E A; Gearhart, J M; Sterner, T R; Robinson, P J

2008-07-01

n-Decane is considered a major component of various fuels and industrial solvents. These hydrocarbon products are complex mixtures of hundreds of components, including straight-chain alkanes, branched chain alkanes, cycloalkanes, diaromatics, and naphthalenes. Human exposures to the jet fuel, JP-8, or to industrial solvents in vapor, aerosol, and liquid forms all have the potential to produce health effects, including immune suppression and/or neurological deficits. A physiologically based pharmacokinetic (PBPK) model has previously been developed for n-decane, in which partition coefficients (PC), fitted to 4-h exposure kinetic data, were used in preference to measured values. The greatest discrepancy between fitted and measured values was for fat, where PC values were changed from 250-328 (measured) to 25 (fitted). Such a large change in a critical parameter, without any physiological basis, greatly impedes the model's extrapolative abilities, as well as its applicability for assessing the interactions of n-decane or similar alkanes with other compounds in a mixture model. Due to these limitations, the model was revised. Our approach emphasized the use of experimentally determined PCs because many tissues had not approached steady-state concentrations by the end of the 4-h exposures. Diffusion limitation was used to describe n-decane kinetics for the brain, perirenal fat, skin, and liver. Flow limitation was used to describe the remaining rapidly and slowly perfused tissues. As expected from the high lipophilicity of this semivolatile compound (log K(ow) = 5.25), sensitivity analyses showed that parameters describing fat uptake were next to blood:air partitioning and pulmonary ventilation as critical in determining overall systemic circulation and uptake in other tissues. In our revised model, partitioning into fat took multiple days to reach steady state, which differed considerably from the previous model that assumed steady-state conditions in fat at 4 h post dosing with 1200 ppm. Due to these improvements, and particularly the reconciliation between measured and fitted partition coefficients, especially fat, we have greater confidence in using the proposed model for dose, species, and route of exposure extrapolations and as a harmonized model approach for other hydrocarbon components of mixtures.

Using mixed solvent and changing spin-coating parameters to increase the efficiency and lifetime of organic solar cells.

PubMed

Tsai, Yu Sheng; Chu, Wei-Ping; Tang, Rong-Ming; Juang, Fuh-Shyang; Chang, Ming-Hua; Liu, Mark O; Hsieh, Tsung-Eong

2008-10-01

The derivative of C60, i.e., PCBM, and P3HT (3-hexylthiophene) were dissolved in chloroform:dichlorobenzene mixed solvent, then spin-coated as the active layer for organic solar cells (OSC). The experimental parameters were studied carefully to obtain the optimum power conversion efficiency (PCE), including the solvent mixing ratio, spin-coating speed, annealing conditions for the active layer, etc. The OSC devices were packaged with glass and a newly developed UV-glue to improve the lifetime and PCE. Dichlorobenzene solvent has great effect upon the PCE. Changing the spin-coating speed and increasing the number of steps increased the PCE apparently to 1.4%.

The role of the attractive and the repulsive interactions in the nonpolar solvation dynamics in simple fluids from the gas-like to the liquid-like densities

NASA Astrophysics Data System (ADS)

Yamaguchi, T.; Kimura, Y.; Hirota, N.

1999-09-01

We have performed molecular dynamics (MD) simulations of the nonpolar solvation dynamics in simple fluids composed of particles interacting through the Lennard-Jones (LJ) 12-6 potential or its repulsive part. The attractive or the repulsive part of the solute-solvent interaction is assumed to change on the excitation of a solute. We have followed the transition energy fluctuation of the solute by the equilibrium simulation. The division of the LJ potential followed the method of WCA [J. W. Weeks, D. Chandler, and H. C. Andersen, J. Chem. Phys. 54, 5237 (1971)]. We have surveyed over a wide solvent density region from gas-like to liquid-like densities at the constant temperature. When the attractive part changes, the relaxation becomes faster with an increase of the solvent density. This result contradicts with previous theories that treat the nonpolar solvation dynamics in terms of the diffusion of solvent particles. The time scale of the initial part of the relaxation is well correlated with the static fluctuation divided by the static average, which suggests the importance of the curvature of the free energy surface in the initial part of the solvation. When the repulsive part changes, the initial part of the relaxation is almost density independent, determined by the binary motion between solute and solvent. It is consistent with the result that the static fluctuation is almost proportional to the static average, which indicates the absence of the static correlation between solvent particles. On the other hand, the solvation correlation function shows rather complicated density dependence at the longer time scale. In the case of the binary mixture solvent, the relaxation time is inversely proportional to the diffusion coefficient. On the basis of the nonpolar solvation dynamics, the validity of the isolated binary collision model for the vibrational energy relaxation is also discussed, and the recent hydrodynamic theory on the vibrational energy relaxation [B. J. Cherayil and M. D. Feyer, J. Chem. Phys. 107, 7642 (1997)] is critically examined.

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

Next Generation Solvent Performance in the Modular Caustic Side Solvent Extraction Process - 15495

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

Smith, Tara E.; Scherman, Carl; Martin, David

Changes to the Modular Caustic Side Solvent Extraction Unit (MCU) flow-sheet were implemented in the facility. Implementation included changing the scrub and strip chemicals and concentrations, modifying the O/A ratios for the strip, scrub, and extraction contactor banks, and blending the current BoBCalixC6 extractant-based solvent in MCU with clean MaxCalix extractant-based solvent. During the successful demonstration period, the MCU process was subject to rigorous oversight to ensure hydraulic stability and chemical/radionuclide analysis of the key process tanks (caustic wash tank, solvent hold tank, strip effluent hold tank, and decontaminated salt solution hold tank) to evaluate solvent carryover to downstream facilitiesmore » and the effectiveness of cesium removal from the liquid salt waste. Results indicated the extraction of cesium was significantly more effective with an average Decontamination Factor (DF) of 1,129 (range was 107 to 1,824) and that stripping was effective. The contactor hydraulic performance was stable and satisfactory, as indicated by contactor vibration, contactor rotational speed, and flow stability; all of which remained at or near target values. Furthermore, the Solvent Hold Tank (SHT) level and specific gravity was as expected, indicating that solvent integrity and organic hydraulic stability were maintained. The coalescer performances were in the range of processing results under the BOBCalixC6 flow sheet, indicating negligible adverse impact of NGS deployment. After the Demonstration period, MCU began processing via routine operations. Results to date reiterate the enhanced cesium extraction and stripping capability of the Next Generation Solvent (NGS) flow sheet. This paper presents process performance results of the NGS Demonstration and continued operations of MCU utilizing the blended BobCalixC6-MaxCalix solvent under the NGS flowsheet.« less

Hand portable thin-layer chromatography system

DOEpatents

Haas, Jeffrey S.; Kelly, Fredrick R.; Bushman, John F.; Wiefel, Michael H.; Jensen, Wayne A.

2000-01-01

A hand portable, field-deployable thin-layer chromatography (TLC) unit and a hand portable, battery-operated unit for development, illumination, and data acquisition of the TLC plates contain many miniaturized features that permit a large number of samples to be processed efficiently. The TLC unit includes a solvent tank, a holder for TLC plates, and a variety of tool chambers for storing TLC plates, solvent, and pipettes. After processing in the TLC unit, a TLC plate is positioned in a collapsible illumination box, where the box and a CCD camera are optically aligned for optimal pixel resolution of the CCD images of the TLC plate. The TLC system includes an improved development chamber for chemical development of TLC plates that prevents solvent overflow.

Illumination box and camera system

DOEpatents

Haas, Jeffrey S.; Kelly, Fredrick R.; Bushman, John F.; Wiefel, Michael H.; Jensen, Wayne A.; Klunder, Gregory L.

2002-01-01

A hand portable, field-deployable thin-layer chromatography (TLC) unit and a hand portable, battery-operated unit for development, illumination, and data acquisition of the TLC plates contain many miniaturized features that permit a large number of samples to be processed efficiently. The TLC unit includes a solvent tank, a holder for TLC plates, and a variety of tool chambers for storing TLC plates, solvent, and pipettes. After processing in the TLC unit, a TLC plate is positioned in a collapsible illumination box, where the box and a CCD camera are optically aligned for optimal pixel resolution of the CCD images of the TLC plate. The TLC system includes an improved development chamber for chemical development of TLC plates that prevents solvent overflow.

A combination of solvent extraction and freeze thaw for oil recovery from petroleum refinery wastewater treatment pond sludge.

PubMed

Hu, Guangji; Li, Jianbing; Hou, Haobo

2015-01-01

A combination of solvent extraction and freeze thaw was examined for recovering oil from the high-moisture petroleum refinery wastewater treatment pond sludge. Five solvents including cyclohexane (CHX), dichloromethane (DCM), methyl ethyl ketone (MEK), ethyl acetate (EA), and 2-propanol (2-Pro) were examined. It was found that these solvents except 2-Pro showed a promising oil recovery rate of about 40%, but the recycling of DCM solvent after oil extraction was quite low. Three solvents (CHX, MEK and EA) were then selected for examining the effect of freeze/thaw treatment on improving the quality of recovered oil. This treatment increased the total petroleum hydrocarbon (TPH) content in recovered oil from about 40% to 60% for both MEK and EA extractions, but little effect was observed for CHX extraction. Although the solid residue after oil recovery had a significantly decreased TPH content, a high concentration of heavy metals was observed, indicating that this residue may require proper management. In general, the combination of solvent extraction with freeze/thaw is effective for high-moisture oily hazardous waste treatment. Copyright © 2014 Elsevier B.V. All rights reserved.

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.

Occupational exposure to solvents, metals and welding fumes and risk of Parkinson's disease.

PubMed

van der Mark, Marianne; Vermeulen, Roel; Nijssen, Peter C G; Mulleners, Wim M; Sas, Antonetta M G; van Laar, Teus; Huss, Anke; Kromhout, Hans

2015-06-01

The aim of this study was to investigate the potential association between occupational exposure to solvents, metals and/or welding fumes and risk of developing Parkinson's disease (PD). Data of a hospital based case-control study including 444 PD patients and 876 age and sex matched controls was used. Occupational histories and lifestyle information of cases and controls were collected in a structured telephone interview. Exposures to aromatic solvents, chlorinated solvents and metals were estimated by linking the ALOHA+ job-exposure matrix to the occupational histories. Exposure to welding fumes was estimated using self-reported information on welding activities. No statistically significant associations with any of the studied metal and solvent exposures were found. However, for self-reported welding activities we observed non-statistically significant reduced risk estimates (third tertile cumulative exposure: OR = 0.51 (95% CI: 0.21-1.24)). The results of our study did not provide support for an increased chance on developing PD after occupational exposure to aromatic solvents, chlorinated solvents or exposure to metals. The results showed reduced risk estimates for welding, which is in line with previous research, but no clear explanation for these findings is available. Copyright © 2015 Elsevier Ltd. All rights reserved.

Solvent effects on the crystal growth structure and morphology of the pharmaceutical dirithromycin

NASA Astrophysics Data System (ADS)

Wang, Yuan; Liang, Zuozhong

2017-12-01

Solvent effects on the crystal structure and morphology of pharmaceutical dirithromycin molecules were systematically investigated using both experimental crystallization and theoretical simulation. Dirithromycin is one of the new generation of macrolide antibiotics with two polymorphic forms (Form I and Form II) and many solvate forms. Herein, six solvates of the dirithromycin, including acetonitrile, acetonitrile/water, acetone, 1-propanol, N,N-dimethylformamide (DMF) and cyclohexane, were studied. Experimentally, we crystallized the dirithromycin molecules in different solvents by the solvent evaporating method and measured the crystal structures with the X-ray diffraction (XRD). We compared these crystal structures of dirithromycin solvates and analyzed the solvent property-determined structure evolution. The solvents have a strong interaction with the dirithromycin molecule due to the formation of inter-molecular interactions (such as the hydrogen bonding and close contacts (sum of vdW radii)). Theoretically, we calculated the ideal crystal habit based on the solvated structures with the attachment growth (AE) model. The predicted morphologies and aspect ratios of dirithromycin solvates agree well with the experimental results. This work could be helpful to better understand the structure and morphology evolution of solvates controlled by solvents and guide the crystallization of active pharmaceutical ingredients in the pharmaceutical industry.

Fast automated dual-syringe based dispersive liquid-liquid microextraction coupled with gas chromatography-mass spectrometry for the determination of polycyclic aromatic hydrocarbons in environmental water samples.

PubMed

Guo, Liang; Tan, Shufang; Li, Xiao; Lee, Hian Kee

2016-03-18

An automated procedure, combining low density solvent based solvent demulsification dispersive liquid-liquid microextraction (DLLME) with gas chromatography-mass spectrometry analysis, was developed for the determination of polycyclic aromatic hydrocarbons (PAHs) in environmental water samples. Capitalizing on a two-rail commercial autosampler, fast solvent transfer using a large volume syringe dedicated to the DLLME process, and convenient extract collection using a small volume microsyringe for better GC performance were enabled. Extraction parameters including the type and volume of extraction solvent, the type and volume of dispersive solvent and demulsification solvent, extraction and demulsification time, and the speed of solvent injection were investigated and optimized. Under the optimized conditions, the linearity ranged from 0.1 to 50 μg/L, 0.2 to 50 μg/L, and 0.5 to 50 μg/L, depending on the analytes. Limits of detection were determined to be between 0.023 and 0.058 μg/L. The method was applied to determine PAHs in environmental water samples. Copyright © 2016 Elsevier B.V. All rights reserved.

Quality by design case study 1: Design of 5-fluorouracil loaded lipid nanoparticles by the W/O/W double emulsion - Solvent evaporation method.

PubMed

Amasya, Gulin; Badilli, Ulya; Aksu, Buket; Tarimci, Nilufer

2016-03-10

With Quality by Design (QbD), a systematic approach involving design and development of all production processes to achieve the final product with a predetermined quality, you work within a design space that determines the critical formulation and process parameters. Verification of the quality of the final product is no longer necessary. In the current study, the QbD approach was used in the preparation of lipid nanoparticle formulations to improve skin penetration of 5-Fluorouracil, a widely-used compound for treating non-melanoma skin cancer. 5-Fluorouracil-loaded lipid nanoparticles were prepared by the W/O/W double emulsion - solvent evaporation method. Artificial neural network software was used to evaluate the data obtained from the lipid nanoparticle formulations, to establish the design space, and to optimize the formulations. Two different artificial neural network models were developed. The limit values of the design space of the inputs and outputs obtained by both models were found to be within the knowledge space. The optimal formulations recommended by the models were prepared and the critical quality attributes belonging to those formulations were assigned. The experimental results remained within the design space limit values. Consequently, optimal formulations with the critical quality attributes determined to achieve the Quality Target Product Profile were successfully obtained within the design space by following the QbD steps. Copyright © 2016 Elsevier B.V. All rights reserved.

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

Ghosh, Soumya; Soudackov, Alexander V.; Hammes-Schiffer, Sharon

Electron transfer and proton coupled electron transfer (PCET) reactions at electrochemical interfaces play an essential role in a broad range of energy conversion processes. The reorganization energy, which is a measure of the free energy change associated with solute and solvent rearrangements, is a key quantity for calculating rate constants for these reactions. We present a computational method for including the effects of the double layer and ionic environment of the diffuse layer in calculations of electrochemical solvent reorganization energies. This approach incorporates an accurate electronic charge distribution of the solute within a molecular-shaped cavity in conjunction with a dielectricmore » continuum treatment of the solvent, ions, and electrode using the integral equations formalism polarizable continuum model. The molecule-solvent boundary is treated explicitly, but the effects of the electrode-double layer and double layer-diffuse layer boundaries, as well as the effects of the ionic strength of the solvent, are included through an external Green’s function. The calculated total reorganization energies agree well with experimentally measured values for a series of electrochemical systems, and the effects of including both the double layer and ionic environment are found to be very small. This general approach was also extended to electrochemical PCET and produced total reorganization energies in close agreement with experimental values for two experimentally studied PCET systems. This research was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center, funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences.« less

The importance of excluded solvent volume effects in computing hydration free energies.

PubMed

Yang, Pei-Kun; Lim, Carmay

2008-11-27

Continuum dielectric methods such as the Born equation have been widely used to compute the electrostatic component of the solvation free energy, DeltaG(solv)(elec), because they do not need to include solvent molecules explicitly and are thus far less costly compared to molecular simulations. All of these methods can be derived from Gauss Law of Maxwell's equations, which yields an analytical solution for the solvation free energy, DeltaG(Born), when the solute is spherical. However, in Maxwell's equations, the solvent is assumed to be a structureless continuum, whereas in reality, the near-solute solvent molecules are highly structured unlike far-solute bulk solvent. Since we have recently reformulated Gauss Law of Maxwell's equations to incorporate the near-solute solvent structure by considering excluded solvent volume effects, we have used it in this work to derive an analytical solution for the hydration free energy of an ion. In contrast to continuum solvent models, which assume that the normalized induced solvent electric dipole density P(n) is constant, P(n) mimics that observed from simulations. The analytical formula for the ionic hydration free energy shows that the Born radius, which has been used as an adjustable parameter to fit experimental hydration free energies, is no longer ill defined but is related to the radius and polarizability of the water molecule, the hydration number, and the first peak position of the solute-solvent radial distribution function. The resulting DeltaG(solv)(elec) values are shown to be close to the respective experimental numbers.

Development of solvent-free ambient mass spectrometry for green chemistry applications.

PubMed

Liu, Pengyuan; Forni, Amanda; Chen, Hao

2014-04-15

Green chemistry minimizes chemical process hazards in many ways, including eliminating traditional solvents or using alternative recyclable solvents such as ionic liquids. This concept is now adopted in this study for monitoring solvent-free reactions and analysis of ionic liquids, solids, and catalysts by mass spectrometry (MS), without using any solvent. In our approach, probe electrospray ionization (PESI), an ambient ionization method, was employed for this purpose. Neat viscous room-temperature ionic liquids (RTILs) in trace amounts (e.g., 25 nL) could be directly analyzed without sample carryover effect, thereby enabling high-throughput analysis. With the probe being heated, it can also ionize ionic solid compounds such as organometallic complexes as well as a variety of neat neutral solid chemicals (e.g., amines). More importantly, moisture-sensitive samples (e.g., [bmim][AlCl4]) can be successfully ionized. Furthermore, detection of organometallic catalysts (including air-sensitive [Rh-MeDuPHOS][OTf]) in ionic liquids, a traditionally challenging task due to strong ion suppression effect from ionic liquids, can be enabled using PESI. In addition, PESI can be an ideal approach for monitoring solvent-free reactions. Using PESI-MS, we successfully examined the alkylation of amines by alcohols, the conversion of pyrylium into pyridinium, and the condensation of aldehydes with indoles as well as air- and moisture-sensitive reactions such as the oxidation of ferrocene and the condensation of pyrazoles with borohydride. Interestingly, besides the expected reaction products, the reaction intermediates such as the monopyrazolylborate ion were also observed, providing insightful information for reaction mechanisms. We believe that the presented solvent-free PESI-MS method would impact the green chemistry field.

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

NASA Astrophysics Data System (ADS)

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

2015-12-01

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

Fabrication and characterization of poly(L-lactic acid) gels induced by fibrous complex crystallization with solvents

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

Matsuda, Yasuhiro; Fukatsu, Akinobu; Wang, Yangyang

2014-01-01

Complex crystal induced gelation of poly(L-lactic acid) (PLLA) solutions was studied for a series of solvents, including N,N-dimethylformamide (DMF). By cooling the solutions prepared at elevated temperatures, PLLA gels were produced in solvents that induced complex crystals ( -crystals) with PLLA. Fibrous structure of PLLA in the gel with DMF was observed by polarizing optical microscopy, field emission electron microscopy, and atomic force microscopy. Upon heating, the crystal form of PLLA in the DMF gel changed from -crystal to a-crystal, the major crystal form in common untreated PLLA films, but the morphology and high elastic modulus of the gel remainedmore » until the a-crystal dissolved at higher temperature. In addition, a solvent exchanging method was developed, which allowed PLLA gels to be prepared in other useful solvents that do not induce -crystals without losing the morphology and mechanical properties.« less

Method for producing metal oxide aerogels

DOEpatents

Tillotson, Thomas M.; Poco, John F.; Hrubesh, Lawrence W.; Thomas, Ian M.

1995-01-01

A two-step hydrolysis-condensation method was developed to form metal oxide aerogels of any density, including densities of less than 0.003g/cm.sup.3 and greater than 0.27g/cm.sup.3. High purity metal alkoxide is reacted with water, alcohol solvent, and an additive to form a partially condensed metal intermediate. All solvent and reaction-generated alcohol is removed, and the intermediate is diluted with a nonalcoholic solvent. The intermediate can be stored for future use to make aerogels of any density. The aerogels are formed by reacting the intermediate with water, nonalcoholic solvent, and a catalyst, and extracting the nonalcoholic solvent directly. The resulting monolithic aerogels are hydrophobic and stable under atmospheric conditions, and exhibit good optical transparency, high clarity, and homogeneity. The aerogels have high thermal insulation capacity, high porosity, mechanical strength and stability, and require shorter gelation times than aerogels formed by conventional methods.

Comparison of extraction techniques and modeling of accelerated solvent extraction for the authentication of natural vanilla flavors.

PubMed

Cicchetti, Esmeralda; Chaintreau, Alain

2009-06-01

Accelerated solvent extraction (ASE) of vanilla beans has been optimized using ethanol as a solvent. A theoretical model is proposed to account for this multistep extraction. This allows the determination, for the first time, of the total amount of analytes initially present in the beans and thus the calculation of recoveries using ASE or any other extraction technique. As a result, ASE and Soxhlet extractions have been determined to be efficient methods, whereas recoveries are modest for maceration techniques and depend on the solvent used. Because industrial extracts are obtained by many different procedures, including maceration in various solvents, authenticating vanilla extracts using quantitative ratios between the amounts of vanilla flavor constituents appears to be unreliable. When authentication techniques based on isotopic ratios are used, ASE is a valid sample preparation technique because it does not induce isotopic fractionation.

Method for producing metal oxide aerogels

DOEpatents

Tillotson, T.M.; Poco, J.F.; Hrubesh, L.W.; Thomas, I.M.

1995-04-25

A two-step hydrolysis-condensation method was developed to form metal oxide aerogels of any density, including densities of less than 0.003g/cm{sup 3} and greater than 0.27g/cm{sup 3}. High purity metal alkoxide is reacted with water, alcohol solvent, and an additive to form a partially condensed metal intermediate. All solvent and reaction-generated alcohol is removed, and the intermediate is diluted with a nonalcoholic solvent. The intermediate can be stored for future use to make aerogels of any density. The aerogels are formed by reacting the intermediate with water, nonalcoholic solvent, and a catalyst, and extracting the nonalcoholic solvent directly. The resulting monolithic aerogels are hydrophobic and stable under atmospheric conditions, and exhibit good optical transparency, high clarity, and homogeneity. The aerogels have high thermal insulation capacity, high porosity, mechanical strength and stability, and require shorter gelation times than aerogels formed by conventional methods. 8 figs.

Molecular Origins of Internal Friction Effects on Protein Folding Rates

PubMed Central

Sirur, Anshul

2014-01-01

Recent experiments on protein folding dynamics have revealed strong evidence for internal friction effects. That is, observed relaxation times are not simply proportional to the solvent viscosity as might be expected if the solvent were the only source of friction. However, a molecular interpretation of this remarkable phenomenon is currently lacking. Here, we use all-atom simulations of peptide and protein folding in explicit solvent, to probe the origin of the unusual viscosity dependence. We find that an important contribution to this effect, explaining the viscosity dependence of helix formation and the folding of a helix-containing protein, is the insensitivity of torsion angle isomerization to solvent friction. The influence of this landscape roughness can, in turn, be quantitatively explained by a rate theory including memory friction. This insensitivity of local barrier crossing to solvent friction is expected to contribute to the viscosity dependence of folding rates in larger proteins. PMID:24986114

Molecular origins of internal friction effects on protein-folding rates.

PubMed

de Sancho, David; Sirur, Anshul; Best, Robert B

2014-07-02

Recent experiments on protein-folding dynamics have revealed strong evidence for internal friction effects. That is, observed relaxation times are not simply proportional to the solvent viscosity as might be expected if the solvent were the only source of friction. However, a molecular interpretation of this remarkable phenomenon is currently lacking. Here, we use all-atom simulations of peptide and protein folding in explicit solvent, to probe the origin of the unusual viscosity dependence. We find that an important contribution to this effect, explaining the viscosity dependence of helix formation and the folding of a helix-containing protein, is the insensitivity of torsion angle isomerization to solvent friction. The influence of this landscape roughness can, in turn, be quantitatively explained by a rate theory including memory friction. This insensitivity of local barrier crossing to solvent friction is expected to contribute to the viscosity dependence of folding rates in larger proteins.

Regimes of electrostatic collapse of a highly charged polyelectrolyte in a poor solvent.

PubMed

Tom, Anvy Moly; Vemparala, Satyavani; Rajesh, R; Brilliantov, Nikolai V

2017-03-01

We perform extensive molecular dynamics simulations of a highly charged, collapsed, flexible polyelectrolyte chain in a poor solvent for the case when the electrostatic interactions, characterized by the reduced Bjerrum length l B , are strong. We find the existence of several sub-regimes in the dependence of the gyration radius of the chain R g on l B characterized by R g ∼ l. In contrast to a good solvent, the exponent γ for a poor solvent crucially depends on the size and valency of the counterions. To explain the different sub-regimes, we generalize the existing counterion fluctuation theory by including a more complete account of all possible volume interactions in the free energy of the polyelectrolyte chain. We also show that the presence of condensed counterions modifies the effective attraction among the chain monomers and modulates the sign of the second virial coefficient under poor solvent conditions.

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

NASA Technical Reports Server (NTRS)

Izmailov, Alexander F.; Myerson, Allan S.

1993-01-01

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

Revisiting Hansen Solubility Parameters by Including Thermodynamics.

PubMed

Louwerse, Manuel J; Maldonado, Ana; Rousseau, Simon; Moreau-Masselon, Chloe; Roux, Bernard; Rothenberg, Gadi

2017-11-03

The Hansen solubility parameter approach is revisited by implementing the thermodynamics of dissolution and mixing. Hansen's pragmatic approach has earned its spurs in predicting solvents for polymer solutions, but for molecular solutes improvements are needed. By going into the details of entropy and enthalpy, several corrections are suggested that make the methodology thermodynamically sound without losing its ease of use. The most important corrections include accounting for the solvent molecules' size, the destruction of the solid's crystal structure, and the specificity of hydrogen-bonding interactions, as well as opportunities to predict the solubility at extrapolated temperatures. Testing the original and the improved methods on a large industrial dataset including solvent blends, fit qualities improved from 0.89 to 0.97 and the percentage of correct predictions rose from 54 % to 78 %. Full Matlab scripts are included in the Supporting Information, allowing readers to implement these improvements on their own datasets. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hydrogen interactions with metals

NASA Technical Reports Server (NTRS)

Mclellan, R. B.; Harkins, C. G.

1975-01-01

Review of the literature on the nature and extent of hydrogen interactions with metals and the role of hydrogen in metal failure. The classification of hydrogen-containing systems is discussed, including such categories as covalent hydrides, volatile hydrides, polymeric hydrides, and transition metal hydride complexes. The use of electronegativity as a correlating parameter in determining hydride type is evaluated. A detailed study is made of the thermodynamics of metal-hydrogen systems, touching upon such aspects as hydrogen solubility, the positions occupied by hydrogen atoms within the solvent metal lattice, the derivation of thermodynamic functions of solid solutions from solubility data, and the construction of statistical models for hydrogen-metal solutions. A number of theories of hydrogen-metal bonding are reviewed, including the rigid-band model, the screened-proton model, and an approach employing the augmented plane wave method to solve the one-electron energy band problem. Finally, the mechanism of hydrogen embrittlement is investigated on the basis of literature data concerning stress effects and the kinetics of hydrogen transport to critical sites.

Aqueous alternatives for metal and composite cleaning

NASA Technical Reports Server (NTRS)

Quitmeyer, Joann

1994-01-01

For many years the metalworking industry has cleaned metal and composite substrates with chlorinated solvents. Recently, however, health and disposal related environmental concerns have increased regarding chlorinated solvents, including 1,1,1-trichloroethane, trichloroethylene, methylene chloride, or Freon'. World leaders have instituted a production ban of certain ozone depleting chlorofluorocarbons (CFC's) by 1996. The Occupational Safety and Health Administration (OSHA) has instituted worker vapor exposure limitations for virtually all of the solvents used in solvent-based cleaners. In addition, the United States Environmental Protection Agency (EPA) has defined nearly all solvent-based cleaners as 'hazardous'. Cradle to grave waste responsibility is another reason manufacturers are trying to replace chlorinated solvents in their cleaning processes. Because of these factors, there now is a world wide effort to reduce and/or eliminate the use of chlorinated solvents for industrial cleaning. Waterbased cleaners are among the alternatives being offered to the industry. New technology alkaline cleaners are now available that can be used instead of chlorinated solvents in many cleaning processes. These waterbased cleaners reduce the release of volatile organic compounds (VOC's) by as much as 99 percent. (The definition and method of calculation of VOC's now varies from region to region.) Hazardous waste generation can also be significantly reduced or eliminated with new aqueous technology. This in turn can ease worker exposure restrictions and positively impact the environment. This paper compares the chemical and physical properties of this aqueous cleaners versus chlorinated solvents.

Tipping Point for Expansion of Layered Aluminosilicates in Weakly Polar Solvents: Supercritical CO 2

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

Schaef, Herbert T.; Loganathan, Narasimhan; Bowers, Geoffrey M.

Layered aluminosilicates play a dominant role in the mechanical and gas storage properties of the subsurface, are used in diverse industrial applications, and serve as model materials for understanding solvent-ion-support systems. Although expansion in the presence of H2O is well known to be systematically correlated with the hydration free energy of the interlayer cation, in environments dominated by non-polar solvents (i.e. CO2), uptake into the interlayer is not well-understood. Using novel high pressure capabilities, we investigated the interaction of super-critical CO2 with Na+-, NH4+-, and Cs+-saturated montmorillonite, comparing results with predictions from molecular dynamics simulations. Despite the known trend inmore » H2O, and that cation solvation energies in CO2 suggest a stronger interaction with Na+, both the NH4+- and Cs+-clays readily absorbed CO2 and expanded while the Na+-clay did not. The apparent inertness of the Na+-clay was not due to kinetics, as experiments seeking a stable expanded state showed that none exists. Molecular dynamics simulations revealed a large endothermicity to CO2 intercalation in the Na+-clay, but little or no energy barrier for the NH4+- and Cs+-clays. Consequently, we have shown for the first time that in the presence of a low dielectric constant gas swelling depends more on the strength of the interaction between interlayer cation and aluminosilicate sheets and less on that with solvent. The finding suggests a distinct regime in layered aluminosilicates swelling behavior triggered by low solvent polarizability, with important implications in geomechanics, storage and retention of volatile gases, and across industrial uses in gelling, decoloring, heterogeneous catalysis, and semi-permeable reactive barriers.« less

The Effects of Organic Solvents on the Physicochemical Properties of Human Serum Albumin Nanoparticles

PubMed Central

Mohammad-Beigi, Hossein; Shojaosadati, Seyed Abbas; Morshedi, Dina; Mirzazadeh, Negar; Arpanaei, Ayyoob

2016-01-01

Background Recently, applications of albumin nanoparticles as drug delivery carriers have increased. Most toxicology studies have shown that surface chemistry and size of nanoparticles play an important role in biocompatibility and toxicity. Objective The effect of desolvating agents with different chemical properties on the size of synthesized HSA NPs was investigated. Materials and Methods Acetone, ethanol, methanol, and acetonitrile were used to synthesize HSA NPs with controllable size by desolvation method. Scanning electron microscopy (SEM), dynamic light scattering (DLS), and circular dichroism (CD) were employed to characterize produced particles. Finally, the toxicity of HSA NPs synthesized under different conditions was evaluated on PC-12 cells. Results The sizes of synthesized particles differed according to the different solvents used. The sizes were 275.3 nm, 155.3 nm, 100.11 nm, and 66.2 nm for acetonitrile, ethanol, acetone, and methanol, respectively. CD showed that larger NPs had more changes in the secondary structures. Finally, the toxicity monitored on the cultured PC-12 cells showed no significant toxic effect through treating with these NPs at different concentrations (0-500 μg.mL-1). Conclusions The size of HSA NPs has a strong dependency on the desolvating agent. The mechanism in which the desolvating agent affects the size of HSA NPs is complex. Various factors such as dielectric constant, polarity, functional groups, and hydrogen bonding of the solvents have the potential to affect the size and structure of HSA NPs. CD analysis suggested that the solvent denaturing capability had a critical effect on the HSA particle size. The stronger denaturing capability of the solvent resulted in the larger HSA particle size. PMID:28959317

The Importance of Water for High Fidelity Information Processing and for Life

NASA Technical Reports Server (NTRS)

Hoehler, Tori M.; Pohorille, Andrew

2011-01-01

Is water an absolute prerequisite for life? Life depends on a variety of non-covalent interactions among molecules, the nature of which is determined as much by the solvent in which they occur as by the molecules themselves. Catalysis and information processing, two essential functions of life, require non-covalent molecular recognition with very high specificity. For example, to correctly reproduce a string consisting of 600,000 units of information (e.g ., 600 kilobases, equivalent to the genome of the smallest free living terrestrial organisms) with a 90% success rate requires specificity > 107 : 1 for the target molecule vs. incorrect alternatives. Such specificity requires (i) that the correct molecular association is energetically stabilized by at least 40 kJ/mol relative to alternatives, and (ii) that the system is able to sample among possible states (alternative molecular associations) rapidly enough to allow the system to fall under thermodynamic control and express the energetic stabilization. We argue that electrostatic interactions are required to confer the necessary energetic stabilization vs. a large library of molecular alternatives, and that a solvent with polarity and dielectric properties comparable to water is required for the system to sample among possible states and express thermodynamic control. Electrostatic associations can be made in non-polar solvents, but the resulting complexes are too stable to be "unmade" with sufficient frequency to confer thermodynamic control on the system. An electrostatic molecular complex representing 3 units of information (e.g., 3 base pairs) with specificity > 107 per unit has a stability in non-polar solvent comparable to that of a carbon-carbon bond at room temperature. These considerations suggest that water, or a solvent with properties very like water, is necessary to support high-fidelity information processing, and can therefore be considered a critical prerequisite for life.

Thermochemistry of paddle wheel MOFs: Cu-HKUST-1 and Zn-HKUST-1.

PubMed

Bhunia, Manas K; Hughes, James T; Fettinger, James C; Navrotsky, Alexandra

2013-06-25

Metal-organic framework (MOF) porosity relies upon robust metal-organic bonds to retain structural rigidity upon solvent removal. Both the as-synthesized and activated Cu and Zn polymorphs of HKUST-1 were studied by room temperature acid solution calorimetry. Their enthalpies of formation from dense assemblages (metal oxide (ZnO or CuO), trimesic acid (TMA), and N,N-dimethylformamide (DMF)) were calculated from the calorimetric data. The enthalpy of formation (ΔHf) of the as-synthesized Cu-HKUST-H2O ([Cu3TMA2·3H2O]·5DMF) is -52.70 ± 0.34 kJ per mole of Cu. The ΔHf for Zn-HKUST-DMF ([Zn3TMA2·3DMF]·2DMF) is -54.22 ± 0.57 kJ per mole of Zn. The desolvated Cu-HKUST-dg [Cu3TMA2] has a ΔHf of 16.66 ± 0.51 kJ/mol per mole Cu. The ΔHf for Zn-HKUST-amorph [Zn3TMA2·2DMF] is -3.57 ± 0.21 kJ per mole of Zn. Solvent stabilizes the Cu-HKUST-H2O by -69.4 kJ per mole of Cu and Zn-HKUST-DMF by at least -50.7 kJ per mole of Zn. Such strong chemisorption of solvent is similar in magnitude to the strongly exothermic binding at low coverage for chemisorbed H2O on transition metal oxide nanoparticle surfaces. The strongly exothermic solvent-framework interaction suggests that solvent can play a critical role in obtaining a specific secondary building unit (SBU) topology.

Cross-phase separation of nanowires and nanoparticles

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

Qian, Fang; Duoss, Eric; Han, Jinkyu

In one embodiment, a process includes creating a mixture of an aqueous component, nanowires and nanoparticles, and a hydrophobic solvent and allowing migration of the nanowires to the hydrophobic solvent, where the nanoparticles remain in the aqueous component. Moreover, the nanowires and nanoparticles are in the aqueous component before the migration.

STRATEGIES FOR THE AEROBIC CO-METABOLISM OF CHLORINATED SOLVENTS. (R825689C019)

EPA Science Inventory

Abstract

Recent field and laboratory studies have evaluated the potential for aerobic co-metabolism of chlorinated solvents. Different co-metabolic substrates and different methods of application have been tried, including growing indigenous microbes in situ, an...

Impact of swelling characteristics on the permselective properties of multi-layer composite membranes for water removal from alcohols.

EPA Science Inventory

The removal of water from organic solvents and biofuels, including lower alcohols (i.e., methanol, ethanol, propanol, and butanol), is necessary for the production, blending, and reuse of those organic compounds. Water forms an azeotrope with many hydrophilic solvents, complicati...

SOLVENT EXTRACTION AND SOIL WASHING TREATMENT OF CONTAMINATED SOILS FROM WOOD PRESERVING SITES: BENCH SCALE STUDIES

EPA Science Inventory

Bench-scale solvent extraction and soil washing studies were performed on soil samples obtained from three abandoned wood preserving sites that included in the NPL. The soil samples from these sites were contaminated with high levels of polyaromatic hydrocarbons (PAHs), pentachlo...

Work ability score of solvent-exposed workers.

PubMed

Furu, Heidi; Sainio, Markku; Hyvärinen, Hanna-Kaisa; Kaukiainen, Ari

2018-03-28

Occupational chronic solvent encephalopathy (CSE), characterized by neurocognitive dysfunction, often leads to early retirement. However, only the more severe cases are diagnosed with CSE, and little is known about the work ability of solvent-exposed workers in general. The aim was to study memory and concentration symptoms, work ability and the effect of both solvent-related and non-occupational factors on work ability, in an actively working solvent-exposed population. A questionnaire on exposure and health was sent to 3640 workers in four solvent-exposed fields, i.e. painters and floor-layers, boat builders, printers, and metal workers. The total number of responses was 1730. We determined the work ability score (WAS), a single question item of the Work Ability Index, and studied solvent exposure, demographic factors, Euroquest memory and concentration symptoms, chronic diseases, and employment status using univariate and multivariate analyses. The findings were compared to those of a corresponding national blue-collar reference population (n = 221), and a small cohort of workers with CSE (n = 18). The proportion of workers with memory and concentration symptoms was significantly associated with solvent exposure. The WAS of solvent-exposed workers was lower than that of the national blue-collar reference group, and the difference was significant in the oldest age group (those aged over 60). Solvent-exposed worker's WAS were higher than those of workers diagnosed with CSE. The WAS were lowest among painters and floor-layers, followed by metal workers and printers, and highest among boat builders. The strongest explanatory factors for poor work ability were the number of chronic diseases, age and employment status. Solvent exposure was a weak independent risk factor for reduced WAS, comparable to a level of high alcohol consumption. Even if memory and concentration symptoms were associated with higher solvent exposure, the effect of solvents on self-experienced work ability was relatively weak. This in line with the improved occupational hygiene and reduced solvent exposure levels in industrialized countries, thus the effect may be stronger in high-level exposure environments. As a single question, WAS is easily included, applicable, and recommendable in occupational screening questionnaires.

Physical properties of the HIV-1 capsid from all-atom molecular dynamics simulations

NASA Astrophysics Data System (ADS)

Perilla, Juan R.; Schulten, Klaus

2017-07-01

Human immunodeficiency virus type 1 (HIV-1) infection is highly dependent on its capsid. The capsid is a large container, made of ~1,300 proteins with altogether 4 million atoms. Although the capsid proteins are all identical, they nevertheless arrange themselves into a largely asymmetric structure made of hexamers and pentamers. The large number of degrees of freedom and lack of symmetry pose a challenge to studying the chemical details of the HIV capsid. Simulations of over 64 million atoms for over 1 μs allow us to conduct a comprehensive study of the chemical-physical properties of an empty HIV-1 capsid, including its electrostatics, vibrational and acoustic properties, and the effects of solvent (ions and water) on the capsid. The simulations reveal critical details about the capsid with implications to biological function.

Psychrophiles

NASA Astrophysics Data System (ADS)

Siddiqui, Khawar S.; Williams, Timothy J.; Wilkins, David; Yau, Sheree; Allen, Michelle A.; Brown, Mark V.; Lauro, Federico M.; Cavicchioli, Ricardo

2013-05-01

Psychrophilic (cold-adapted) microorganisms make a major contribution to Earth's biomass and perform critical roles in global biogeochemical cycles. The vast extent and environmental diversity of Earth's cold biosphere has selected for equally diverse microbial assemblages that can include archaea, bacteria, eucarya, and viruses. Underpinning the important ecological roles of psychrophiles are exquisite mechanisms of physiological adaptation. Evolution has also selected for cold-active traits at the level of molecular adaptation, and enzymes from psychrophiles are characterized by specific structural, functional, and stability properties. These characteristics of enzymes from psychrophiles not only manifest in efficient low-temperature activity, but also result in a flexible protein structure that enables biocatalysis in nonaqueous solvents. In this review, we examine the ecology of Antarctic psychrophiles, physiological adaptation of psychrophiles, and properties of cold-adapted proteins, and we provide a view of how these characteristics inform studies of astrobiology.

Phthalimide Copolymer Solar Cells

NASA Astrophysics Data System (ADS)

Xin, Hao; Guo, Xugang; Ren, Guoqiang; Kim, Felix; Watson, Mark; Jenekhe, Samson

2010-03-01

Photovoltaic properties of bulk heterojunction solar cells based on phthalimide donor-acceptor copolymers have been investigated. Due to the strong π-π stacking of the polymers, the state-of-the-art thermal annealing approach resulted in micro-scale phase separation and thus negligible photocurrent. To achieve ideal bicontinuous morphology, different strategies including quickly film drying and mixed solvent for film processing have been explored. In these films, nano-sale phase separation was achieved and a power conversion efficiency of 3.0% was obtained. Absorption and space-charge limited current mobility measurements reveal similar light harvesting and hole mobilities in all the films, indicating that the morphology is the dominant factor determining the photovoltaic performance. Our results demonstrate that for highly crystalline and/or low-solubility polymers, finding a way to prevent polymer aggregation and large scale phase separation is critical to realizing high performance solar cells.

Target specific proteochemometric model development for BACE1 - protein flexibility and structural water are critical in virtual screening.

PubMed

Manoharan, Prabu; Chennoju, Kiranmai; Ghoshal, Nanda

2015-07-01

BACE1 is an attractive target in Alzheimer's disease (AD) treatment. A rational drug design effort for the inhibition of BACE1 is actively pursued by researchers in both academic and pharmaceutical industries. This continued effort led to the steady accumulation of BACE1 crystal structures, co-complexed with different classes of inhibitors. This wealth of information is used in this study to develop target specific proteochemometric models and these models are exploited for predicting the prospective BACE1 inhibitors. The models developed in this study have performed excellently in predicting the computationally generated poses, separately obtained from single and ensemble docking approaches. The simple protein-ligand contact (SPLC) model outperforms other sophisticated high end models, in virtual screening performance, developed during this study. In an attempt to account for BACE1 protein active site flexibility information in predictive models, we included the change in the area of solvent accessible surface and the change in the volume of solvent accessible surface in our models. The ensemble and single receptor docking results obtained from this study indicate that the structural water mediated interactions improve the virtual screening results. Also, these waters are essential for recapitulating bioactive conformation during docking study. The proteochemometric models developed in this study can be used for the prediction of BACE1 inhibitors, during the early stage of AD drug discovery.

Unique organogel formation with macroporous materials constructed by the freeze-drying of aqueous cyclodextrin solutions.

PubMed

Marui, Yasuhiro; Kikuzawa, Akira; Kida, Toshiyuki; Akashi, Mitsuru

2010-07-06

Macroporous cyclodextrin materials (MP-alpha-, beta-, and gamma-CDs) were easily fabricated by the freeze-drying of aqueous solutions of alpha-, beta-, and gamma-CDs. These MP-CDs showed the absorption ability toward various organic solvents and oils to give organogels at ambient temperature. The morphological changes of the MP-CD microstructures were observed through the absorption of organic solvents. In particular, the absorption of polar organic solvents with hydrogen-bond forming ability, including 1,4-dioxane and ethanol, by the MP-CDs caused remarkable morphological changes in the microstructures. The absorption of these polar solvents by MP-alpha- and gamma-CDs resulted in the formation of channel-type assemblies of alpha- and gamma-CDs, respectively.

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

Chunshan Song; Hatcher, P.G.; Saini, A.K.

It has been indicated by DOE COLIRN panel that low-temperature catalytic pretreatment is a promising approach to the development of an improved liquefaction process. This work is a fundamental study on effects of pretreatments on coal structure and reactivity in liquefaction. The main objectives of this project are to study the coal structural changes induced by low-temperature catalytic and thermal pretreatments by using spectroscopic techniques; and to clarify the pretreatment-induced changes in reactivity or convertibility of coals. As the second volume of the final report, here we summarize our work on spectroscopic characterization of four raw coals including two subbituminousmore » coals and two bituminous coals, tetrahydrofuran (THF)-extracted but unreacted coals, the coals (THF-insoluble parts) that have been thermally pretreated. in the absence of any solvents and in the presence of either a hydrogen-donor solvent or a non-donor solvent, and the coals (THF-insoluble parts) that have been catalytically pretreated in the presence of a dispersed Mo sulfide catalyst in the absence of any solvents and in the presence of either a hydrogen-donor solvent or a non-donor solvent.« less

Acquired intolerance to organic solvents and results of vestibular testing

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

Gyntelberg, F.; Vesterhauge, S.; Fog, P.

1986-01-01

Among 160 consecutive patients referred to the Clinic of Occupational Medicine, Rigshospitalet, for symptoms connected with exposure to organic solvents, 20 exhibited symptoms of acquired intolerance to minor amounts of organic solvents. Later, an additional 30 consecutive patients with symptoms of acquired intolerance were included, yielding a total of 43 men and 7 women. The characteristics of the clinical syndrome described are complaints of dizziness, nausea, and weakness after exposure to minimal solvent vapor concentrations. After having tolerated long-term occupational exposure to moderate or high air concentrations of various organic solvents, the patients became intolerant within a short period ofmore » time. Since dizziness was a frequent complaint, we tried to obtain a measure of the patients' complaints using vestibular tests. As a diagnostic test the combined vestibular tests had a sensitivity of 0.55 and a specificity of 0.87. No differences between patients with and without intolerance could be detected by the vestibular tests used. We conclude that acquired intolerance to organic solvents is a new but characteristic and easily recognizable syndrome, often with severe consequences for the patient's working ability.« 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.

New methods for the analysis of the protein-solvent interface

NASA Astrophysics Data System (ADS)

Goodfellow, Julia M.; Pitt, William R.; Smart, Oliver S.; Williams, Mark A.

1995-09-01

The protein-solvent interface is complex and may include solvent channels and cavities as well as the normal surface water molecules. We describe several algorithms for investigating the intra- and inter-molecular interactions of proteins in general but with the aim of developing methods to accurately and definitively characterise the interactions of water and other small ligands with proteins. Specifically, we present the methods which underlie three programs (AQUARIUS2, HOLE and PRO_ACT) which can be used to to look at different aspects of these interactions.

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.

PRODUCTION OF FLUOROCARBONS

DOEpatents

Sarsfield, N.F.

1949-06-21

This patent pertains to a process for recovering fluorocarbons from a liquid mixture of hydrocarbons with partially and completely fluorinated products thereof. It consists of contacting the mxture in the cold with a liquid which is a solvent for the hydrocarbons and which is a nonsolvent for the fluorocarbons, extracting the hydrocarbons, separating the fluorocarbon-containing layer from the solvent-containing layer, and submitting the fluorocarbon layer to fractlonal distillation, to isolate the desired fluorocarbon fraction. Suitable solvents wnich may be used in the process include the lower aliphatic alcohols, and the lower aliphatic ketones.

Evaluation of Solvent Alternatives for Cleaning of Oxygen Systems

NASA Technical Reports Server (NTRS)

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

1999-01-01

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