Sample records for non-aqueous solvents
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ZnS/Zn(O,OH)S-based buffer layer deposition for solar cells
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.
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Enzymes from solvent-tolerant microbes: useful biocatalysts for non-aqueous enzymology.
Gupta, Anshu; Khare, S K
2009-01-01
Solvent-tolerant microbes are a newly emerging class that possesses the unique ability to thrive in the presence of organic solvents. Their enzymes adapted to mediate cellular and metabolic processes in a solvent-rich environment and are logically stable in the presence of organic solvents. Enzyme catalysis in non-aqueous/low-water media is finding increasing applications for the synthesis of industrially important products, namely peptides, esters, and other trans-esterification products. Solvent stability, however, remains a prerequisite for employing enzymes in non-aqueous systems. Enzymes, in general, get inactivated or give very low rates of reaction in non-aqueous media. Thus, early efforts, and even some recent ones, have aimed at stabilization of enzymes in organic media by immobilization, surface modifications, mutagenesis, and protein engineering. Enzymes from solvent-tolerant microbes appear to be the choicest source for studying solvent-stable enzymes because of their unique ability to survive in the presence of a range of organic solvents. These bacteria circumvent the solvent's toxic effects by virtue of various adaptations, e.g. at the level of the cytoplasmic membrane, by degradation and transformation of solvents, and by active excretion of solvents. The recent screening of these exotic microbes has generated some naturally solvent-stable proteases, lipases, cholesterol oxidase, cholesterol esterase, cyclodextrin glucanotransferase, and other important enzymes. The unique properties of these novel biocatalysts have great potential for applications in non-aqueous enzymology for a range of industrial processes.
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Dahanayake, Jayangika N.; Gautam, Devaki N.; Verma, Rajni; Mitchell-Koch, Katie R.
2016-01-01
The use of enzymes in non-aqueous solvents expands the use of biocatalysts to hydrophobic substrates, with the ability to tune selectivity of reactions through solvent selection. Non-aqueous enzymology also allows for fundamental studies on the role of water and other solvents in enzyme structure, dynamics, and function. Molecular dynamics simulations serve as a powerful tool in this area, providing detailed atomic information about the effect of solvents on enzyme properties. However, a common protocol for non-aqueous enzyme simulations does not exist. If you want to simulate enzymes in non-aqueous solutions, how many and which crystallographic waters do you keep? In the present work, this question is addressed by determining which crystallographic water molecules lead most quickly to an equilibrated protein structure. Five different methods of selecting and keeping crystallographic waters are used in order to discover which crystallographic waters lead the protein structure to reach an equilibrated structure more rapidly in organic solutions. It is found that buried waters contribute most to rapid equilibration in organic solvent, with slow-diffusing waters giving similar results. PMID:27403032
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Non-conventional solvents in liquid phase microextraction and aqueous biphasic systems.
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.
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Membrane separation for non-aqueous solution
NASA Astrophysics Data System (ADS)
Widodo, S.; Khoiruddin; Ariono, D.; Subagjo; Wenten, I. G.
2018-01-01
Membrane technology has been widely used in a number of applications competing with conventional technologies in various ways. Despite the enormous applications, they are mainly used for the aqueous system. The use of membrane-based processes in a non-aqueous system is an emerging area. This is because developed membranes are still limited in separations involving aqueous solution which show several drawbacks when implemented in a non-aqueous system. The purpose of this paper is to provide a review of the current application of membrane processes in non-aqueous solutions, such as mineral oil treatment, vegetable oil processing, and organic solvent recovery. Developments of advanced membrane materials for the non-aqueous solutions such as super-hydrophobic and organic solvent resistant membranes are reviewed. In addition, challenges and future outlook of membrane separation for the non-aqueous solution are discussed.
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Partially Fluorinated Solvent as a co-solvent for the Non-aqueous Electrolyte of Li/air Battery
2010-11-11
ether ( MFE ) and tris(2,2,2-trifluoroethyl) phosphite (TTFP), respectively, as a co-solvent for the non-aqueous electrolyte of Li–air battery. Results...fluorinated solvents on the discharge performance of Li–air bat- tery. For this purpose, we here selectmethyl nonafluorobutyl ether ( MFE ) and tris...196, (2011) pgs. 2867-2870 14. ABSTRACT In this workwestudy methyl nonafluorobutyl ether ( MFE ) and tris(2,2,2-trifluoroethyl) phosphite (TTFP
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NASA Astrophysics Data System (ADS)
Murshid, Ghulam; Garg, Sahil
2018-05-01
Amine scrubbing is the state of the art technology for CO2 capture, and solvent selection can significantly reduce the capital and energy cost of the process. Higher energy requirement for aqueous amine based CO2 removal process is still a most important downside preventive its industrial deployment. Therefore, in this study, novel non-aqueous based amino acid salt system consisting of potassium prolinate, ethanol and ethylene glycol has been studied. This work presents initial CO2 solubility study and important physical properties i.e. density of the studied solvent system. Previous work showed that non-aqueous system of potassium prolinate and ethanol has good absorption rates and requires lower energy for solvent regeneration. However, during regeneration, solvent loss issues were found due to lower boiling point of the ethanol. Therefore, ethylene glycol was added into current studied system for enhancing the overall boiling point of the system. The good initial CO2 solubility and low density of studied solvent system offers several advantages as compared to conventional amine solutions.
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Gull, Maheen; Cafferty, Brian J.; Hud, Nicholas V.; Pasek, Matthew A.
2017-01-01
Phosphorylation reactions of glycerol were studied using different inorganic phosphates such as sodium phosphate, trimetaphosphate (a condensed phosphate), and struvite. The reactions were carried out in two non-aqueous solvents: formamide and a eutectic solvent consisting of choline-chloride and glycerol in a ratio of 1:2.5. The glycerol reacted in formamide and in the eutectic solvent with phosphate to yield its phosphorylated derivatives in the presence of silicates such as quartz sand and kaolinite clay. The reactions were carried out by heating glycerol with a phosphate source at 85 °C for one week and were analyzed by 31P-nuclear magnetic resonance (NMR) spectroscopy and mass spectrometry (MS). The yield of the phosphorylated glycerol was improved by the presence of silicates, and reached 90% in some experiments. Our findings further support the proposal that non-aqueous solvents are advantageous for the prebiotic synthesis of biomolecules, and suggest that silicates may have aided in the formation of organophosphates on the prebiotic earth. PMID:28661422
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Redox active polymers and colloidal particles for flow batteries
DOE Office of Scientific and Technical Information (OSTI.GOV)
Gavvalapalli, Nagarjuna; Moore, Jeffrey S.; Rodriguez-Lopez, Joaquin
The invention provides a redox flow battery comprising a microporous or nanoporous size-exclusion membrane, wherein one cell of the battery contains a redox-active polymer dissolved in the non-aqueous solvent or a redox-active colloidal particle dispersed in the non-aqueous solvent. The redox flow battery provides enhanced ionic conductivity across the electrolyte separator and reduced redox-active species crossover, thereby improving the performance and enabling widespread utilization. Redox active poly(vinylbenzyl ethylviologen) (RAPs) and redox active colloidal particles (RACs) were prepared and were found to be highly effective redox species. Controlled potential bulk electrolysis indicates that 94-99% of the nominal charge on different RAPsmore » is accessible and the electrolysis products are stable upon cycling. The high concentration attainable (>2.0 M) for RAPs in common non-aqueous battery solvents, their electrochemical and chemical reversibility, and their hindered transport across porous separators make them attractive materials for non-aqueous redox flow batteries based on size-selectivity.« less
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Probing the Hofmeister series beyond water: Specific-ion effects in non-aqueous solvents
NASA Astrophysics Data System (ADS)
Mazzini, Virginia; Liu, Guangming; Craig, Vincent S. J.
2018-06-01
We present an experimental investigation of specific-ion effects in non-aqueous solvents, with the aim of elucidating the role of the solvent in perturbing the fundamental ion-specific trend. The focus is on the anions: CH3COO->F->Cl->Br->I->ClO4 ->SCN- in the solvents water, methanol, formamide, dimethyl sulfoxide (DMSO), and propylene carbonate (PC). Two types of experiments are presented. The first experiment employs the technique of size exclusion chromatography to evaluate the elution times of electrolytes in the different solvents. We observe that the fundamental (Hofmeister) series is observed in water and methanol, whilst the series is reversed in DMSO and PC. No clear series is observed for formamide. The second experiment uses the quartz crystal microbalance technique to follow the ion-induced swelling and collapse of a polyelectrolyte brush. Here the fundamental series is observed in the protic solvents water, methanol, and formamide, and the series is once again reversed in DMSO and PC. These behaviours are not attributed to the protic/aprotic nature of the solvents, but rather to the polarisability of the solvents and are due to the competition between the interaction of ions with the solvent and the surface. A rule of thumb is proposed for ion specificity in non-aqueous solvents. In weakly polarisable solvents, the trends in specific-ion effects will follow those in water, whereas in strongly polarisable solvents the reverse trend will be observed. Solvents of intermediate polarisability will give weak specific-ion effects.
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Probing the Hofmeister series beyond water: Specific-ion effects in non-aqueous solvents.
Mazzini, Virginia; Liu, Guangming; Craig, Vincent S J
2018-06-14
We present an experimental investigation of specific-ion effects in non-aqueous solvents, with the aim of elucidating the role of the solvent in perturbing the fundamental ion-specific trend. The focus is on the anions: CH 3 COO - >F - >Cl - >Br - >I - >ClO 4 - >SCN - in the solvents water, methanol, formamide, dimethyl sulfoxide (DMSO), and propylene carbonate (PC). Two types of experiments are presented. The first experiment employs the technique of size exclusion chromatography to evaluate the elution times of electrolytes in the different solvents. We observe that the fundamental (Hofmeister) series is observed in water and methanol, whilst the series is reversed in DMSO and PC. No clear series is observed for formamide. The second experiment uses the quartz crystal microbalance technique to follow the ion-induced swelling and collapse of a polyelectrolyte brush. Here the fundamental series is observed in the protic solvents water, methanol, and formamide, and the series is once again reversed in DMSO and PC. These behaviours are not attributed to the protic/aprotic nature of the solvents, but rather to the polarisability of the solvents and are due to the competition between the interaction of ions with the solvent and the surface. A rule of thumb is proposed for ion specificity in non-aqueous solvents. In weakly polarisable solvents, the trends in specific-ion effects will follow those in water, whereas in strongly polarisable solvents the reverse trend will be observed. Solvents of intermediate polarisability will give weak specific-ion effects.
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Non-aqueous cleaning solvent substitution
NASA Technical Reports Server (NTRS)
Meier, Gerald J.
1994-01-01
A variety of environmental, safety, and health concerns exist over use of chlorinated and fluorinated cleaning solvents. Sandia National Laboratories, Lawrence Livermore National Laboratories, and the Kansas City Division of AlliedSignal have combined efforts to focus on finding alternative cleaning solvents and processes which are effective, environmentally safe, and compliant with local, state, and federal regulations. An alternative solvent has been identified, qualified, and implemented into production of complex electronic assemblies, where aqueous and semi-aqueous cleaning processes are not allowed. Extensive compatibility studies were performed with components, piece-parts, and materials. Electrical testing and accelerated aging were used to screen for detrimental, long-term effects. A terpene, d-limonene, was selected as the solvent of choice, and it was found to be compatible with the components and materials tested. A brief history of the overall project will be presented, along with representative cleaning efficiency results, compatibility results, and residual solvent data. The electronics industry is constantly searching for proven methods and environmentally-safe materials to use in manufacturing processes. The information in this presentation will provide another option to consider on future projects for applications requiring high levels of quality, reliability, and cleanliness from non-aqueous cleaning processes.
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Rubinstein, Alexander I; Sabirianov, Renat F; Namavar, Fereydoon
2016-10-14
The rapid development of nanoscience and nanotechnology has raised many fundamental questions that significantly impede progress in these fields. In particular, understanding the physicochemical processes at the interface in aqueous solvents requires the development and application of efficient and accurate methods. In the present work we evaluate the electrostatic contribution to the energy of model protein-ceramic complex formation in an aqueous solvent. We apply a non-local (NL) electrostatic approach that accounts for the effects of the short-range structure of the solvent on the electrostatic interactions of the interfacial systems. In this approach the aqueous solvent is considered as a non-ionic liquid, with the rigid and strongly correlated dipoles of the water molecules. We have found that an ordered interfacial aqueous solvent layer at the protein- and ceramic-solvent interfaces reduces the charging energy of both the ceramic and the protein in the solvent, and significantly increases the electrostatic contribution to their association into a complex. This contribution in the presented NL approach was found to be significantly shifted with respect to the classical model at any dielectric constant value of the ceramics. This implies a significant increase of the adsorption energy in the protein-ceramic complex formation for any ceramic material. We show that for several biocompatible ceramics (for example HfO2, ZrO2, and Ta2O5) the above effect predicts electrostatically induced protein-ceramic complex formation. However, in the framework of the classical continuum electrostatic model (the aqueous solvent as a uniform dielectric medium with a high dielectric constant ∼80) the above ceramics cannot be considered as suitable for electrostatically induced complex formation. Our results also show that the protein-ceramic electrostatic interactions can be strong enough to compensate for the unfavorable desolvation effect in the process of protein-ceramic complex formation.
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NASA Astrophysics Data System (ADS)
Rubinstein, Alexander I.; Sabirianov, Renat F.; Namavar, Fereydoon
2016-10-01
The rapid development of nanoscience and nanotechnology has raised many fundamental questions that significantly impede progress in these fields. In particular, understanding the physicochemical processes at the interface in aqueous solvents requires the development and application of efficient and accurate methods. In the present work we evaluate the electrostatic contribution to the energy of model protein-ceramic complex formation in an aqueous solvent. We apply a non-local (NL) electrostatic approach that accounts for the effects of the short-range structure of the solvent on the electrostatic interactions of the interfacial systems. In this approach the aqueous solvent is considered as a non-ionic liquid, with the rigid and strongly correlated dipoles of the water molecules. We have found that an ordered interfacial aqueous solvent layer at the protein- and ceramic-solvent interfaces reduces the charging energy of both the ceramic and the protein in the solvent, and significantly increases the electrostatic contribution to their association into a complex. This contribution in the presented NL approach was found to be significantly shifted with respect to the classical model at any dielectric constant value of the ceramics. This implies a significant increase of the adsorption energy in the protein-ceramic complex formation for any ceramic material. We show that for several biocompatible ceramics (for example HfO2, ZrO2, and Ta2O5) the above effect predicts electrostatically induced protein-ceramic complex formation. However, in the framework of the classical continuum electrostatic model (the aqueous solvent as a uniform dielectric medium with a high dielectric constant ˜80) the above ceramics cannot be considered as suitable for electrostatically induced complex formation. Our results also show that the protein-ceramic electrostatic interactions can be strong enough to compensate for the unfavorable desolvation effect in the process of protein-ceramic complex formation.
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NASA Astrophysics Data System (ADS)
Mukherji, Debashish; Marques, Carlos M.; Kremer, Kurt
2018-01-01
In this work we discuss two mirror but distinct phenomena of polymer paradoxical properties in mixed solvents: co-non-solvency and co-solvency. When a polymer collapses in a mixture of two miscible good solvents the phenomenon is known as co-non-solvency, while co-solvency is a phenomenon that is associated with the swelling of a polymer in poor solvent mixtures. A typical example of co-non-solvency is provided by poly(N-isopropylacrylamide) in aqueous alcohol, while poly(methyl methacrylate) in aqueous alcohol shows co-solvency. We discuss these two phenomena to compare their microscopic origins and show that both can be understood within generic universal concepts. A broad range of polymers is therefore expected to exhibit these phenomena where specific chemical details play a lesser role than the appropriate combination of interactions between the trio of molecular components.
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Protein-style dynamical transition in a non-biological polymer and a non-aqueous solvent
DOE Office of Scientific and Technical Information (OSTI.GOV)
Mamontov, E.; Sharma, V. K.; Borreguero, J. M.
Using neutron scattering and molecular dynamics simulation, techniques most often associated with protein dynamical transition studies, we have investigated the microscopic dynamics of one of the most common polymers, polystyrene, which was exposed to toluene vapor, mimicking the process of protein hydration from water vapor. Polystyrene with adsorbed toluene is an example of a solvent-solute system, which, unlike biopolymers, is anhydrous and lacks hydrogen bonding. Nevertheless, it exhibits the essential traits of the dynamical transition in biomolecules, such as a specific dependence of the microscopic dynamics of both solvent and host on the temperature and the amount of solvent adsorbed.more » Ultimately, we conclude that the protein dynamical transition is a manifestation of a universal solvent-solute dynamical relationship, which is not specific to either biomolecules as solute, or aqueous media as solvent, or even a particular type of interactions between solvent and solute.« less
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Protein-style dynamical transition in a non-biological polymer and a non-aqueous solvent
Mamontov, E.; Sharma, V. K.; Borreguero, J. M.; ...
2016-03-15
Using neutron scattering and molecular dynamics simulation, techniques most often associated with protein dynamical transition studies, we have investigated the microscopic dynamics of one of the most common polymers, polystyrene, which was exposed to toluene vapor, mimicking the process of protein hydration from water vapor. Polystyrene with adsorbed toluene is an example of a solvent-solute system, which, unlike biopolymers, is anhydrous and lacks hydrogen bonding. Nevertheless, it exhibits the essential traits of the dynamical transition in biomolecules, such as a specific dependence of the microscopic dynamics of both solvent and host on the temperature and the amount of solvent adsorbed.more » Ultimately, we conclude that the protein dynamical transition is a manifestation of a universal solvent-solute dynamical relationship, which is not specific to either biomolecules as solute, or aqueous media as solvent, or even a particular type of interactions between solvent and solute.« less
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Advances in Non-Aqueous Chemistry
ERIC Educational Resources Information Center
Holliday, A. K.; Nicholls, D.
1974-01-01
A discussion concerning the choice of solvents for a chemical reaction is followed by an examination of the advantages of using liquid ammonia, oxide solvents, and molten salts as alternatives to water as a solvent. (DT)
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Lail, Marty
The project aimed to advance RTI’s non-aqueous amine solvent technology by improving the solvent to reduce volatility, demonstrating long-term continuous operation at lab- (0.5 liters solvent) and bench-scale (~120 liters solvent), showing low reboiler heat duty measured during bench-scale testing, evaluating degradation products, building a rate-based process model, and evaluating the techno-economic performance of the process. The project team (RTI, SINTEF, Linde Engineering) and the technology performed well in each area of advancement. The modifications incorporated throughout the project enabled the attainment of target absorber and regenerator conditions for the process. Reboiler duties below 2,000 kJt/kg CO2 were observed inmore » a bench-scale test unit operated at RTI.« less
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Measuring Nitrous Oxide Mass Transfer into Non-Aqueous CO2BOL CO2 Capture Solvents
DOE Office of Scientific and Technical Information (OSTI.GOV)
Whyatt, Greg A.; Freeman, Charles J.; Zwoster, Andy
2016-03-28
This paper investigates CO2 absorption behavior in CO2BOL solvents by decoupling the physical and chemical effects using N2O as a non-reactive mimic. Absorption measurements were performed using a wetted-wall contactor. Testing was performed using a “first generation” CO2 binding organic liquid (CO2BOL), comprised of an independent base and alcohol. Measurements were made with N2O at a lean (0.06 mol CO2/mol BOL) and rich (0.26 mol CO2/mol BOL) loading, each at three temperatures (35, 45 and 55 °C). Liquid-film mass transfer coefficients (kg') were calculated by subtracting the gas film resistance – determined from a correlation from literature – from themore » overall mass transfer measurement. The resulting kg' values for N2O in CO2BOLs were found to be higher than that of 5 M aqueous MEA under comparable conditions, which is supported by published measurements of Henry’s coefficients for N2O in various solvents. These results suggest that the physical solubility contribution for CO2 absorption in CO2BOLs is greater than that of aqueous amines, an effect that may pertain to other non-aqueous solvents.« less
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NASA Technical Reports Server (NTRS)
Williamson, Steve; Aman, Bob; Aurigema, Andrew; Melendez, Orlando
1999-01-01
The Wiltech Component Cleaning & Refurbishment Facility (WT-CCRF) at NASA Kennedy Space Center performs precision cleaning on approximately 200,000 metallic and non metallic components every year. WT-CCRF has developed a CFC elimination plan consisting of aqueous cleaning and verification and an economical dual solvent strategy for alternative solvent solution. Aqueous Verification Methodologies were implemented two years ago on a variety of Ground Support Equipment (GSE) components and sampling equipment. Today, 50% of the current workload is verified using aqueous methods and 90% of the total workload is degreased aqueously using, Zonyl and Brulin surfactants in ultrasonic baths. An additional estimated 20% solvent savings could be achieved if the proposed expanded use of aqueous methods are approved. Aqueous cleaning has shown to be effective, environmentally friendly and economical (i.e.. cost of materials, equipment, facilities and labor).
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NASA Astrophysics Data System (ADS)
Farajtabar, Ali; Jaberi, Fatemeh; Gharib, Farrokh
2011-12-01
The solvatochromic properties of the free base and the protonated 5, 10, 15, 20-tetrakis(4-sulfonatophenyl)porphyrin (TPPS) were studied in pure water, methanol, ethanol (protic solvents), dimethylsulfoxide, DMSO, (non-protic solvent), and their corresponding aqueous-organic binary mixed solvents. The correlation of the empirical solvent polarity scale ( ET) values of TPPS with composition of the solvents was analyzed by the solvent exchange model of Bosch and Roses to clarify the preferential solvation of the probe dyes in the binary mixed solvents. The solvation shell composition and the synergistic effects in preferential solvation of the solute dyes were investigated in terms of both solvent-solvent and solute-solvent interactions and also, the local mole fraction of each solvent composition was calculated in cybotactic region of the probe. The effective mole fraction variation may provide significant physico-chemical insights in the microscopic and molecular level of interactions between TPPS species and the solvent components and therefore, can be used to interpret the solvent effect on kinetics and thermodynamics of TPPS. The obtained results from the preferential solvation and solvent-solvent interactions have been successfully applied to explain the variation of equilibrium behavior of protonation of TPPS occurring in aqueous organic mixed solvents of methanol, ethanol and DMSO.
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Exploratory studies on some electrochemical cell systems
NASA Astrophysics Data System (ADS)
Chaudhuri, Srikumar; Guha, D.
Exploratory studies were conducted on cell systems with different metal anodes, and iodine and sulphur mixed with graphite powder in a polymer matrix as cathodes, using different electrolytes in non-aqueous and aqueous media as ionic charge carriers. The electrical conductance of the electrolyte solutions in aqueous and non-aqueous solvents, the open circuit voltage (OCV) and short circuit current (SCC) for the different cell systems were measured. To date, the non-aqueous solvents used in our studies were dimethylformamide, formamide, dioxan, and nitrobenzene, and the electrolytes used were potassium iodide, caustic potash, cetyltrimethylammonium bromide (CTAB), sodium lauryl sulphate (SLS) and calcium chloride. These electrolytes were used in both non-aqueous and aqueous media. In general, aqueous electrolyte solutions gave a better performance than non-aqueous electrolyte solutions. Of the aqueous electrolytes, the highest conductance was shown by potassium chloride solution in water (conductance=0.0334 mho). However, the best OCV and SCC were shown by aluminium as anode and iodine as cathode with a saturated solution of caustic potash in water. The OCV was 1.85 V and the SCC was 290 mA cm -2. The highest conductance among the non-aqueous systems was shown by caustic potash in formamide. (Conductance=0.013 mho.) The best OCV and SCC, however, were shown by a zinc anode and iodine cathode with saturated potassium chloride in formamide, having an OCV of 1.55 V and an SCC of 150 mA cm -2. Further studies are in progress to obtain detailed performance data and recharging characteristics of some of the more promising systems reported here.
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Zheng, Dong; Yuan, Xiang-Ai; Ma, Haibo; Li, Xiaoxiong; Wang, Xizhang; Liu, Ziteng
2018-01-01
Cresol is a prototype molecule in understanding intermolecular interactions in material and biological systems, because it offers different binding sites with various solvents and protonation states under different pH values. It is found that the UV/Vis absorption spectra of o-cresol in aromatic solvents (benzene, toluene) are characterized by a sharp peak, unlike the broad double-peaks in 11 non-aromatic solvents. Both molecular dynamics simulations and electronic structure calculations revealed the formation of intermolecular π-complexation between o-cresol and aromatic solvents. The thermal movements of solvent and solute molecules render the conformations of o-cresol changing between trans and cis isomers. The π-interaction makes the cis configuration a dominant isomer, hence leading to the single keen-edged UV/Vis absorption peak at approximately 283 nm. The free conformation changes between trans and cis in aqueous solution rationalize the broader absorption peaks in the range of 260–280 nm. The pH dependence of the UV/Vis absorption spectra in aqueous solutions is also rationalized by different protonation states of o-cresol. The explicit solvent model with long-ranged interactions is vital to describe the effects of π-complexation and electrostatic interaction on the UV/Vis absorption spectra of o-cresol in toluene and alkaline aqueous (pH > 10.3) solutions, respectively. PMID:29657794
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Zheng, Dong; Yuan, Xiang-Ai; Ma, Haibo; Li, Xiaoxiong; Wang, Xizhang; Liu, Ziteng; Ma, Jing
2018-03-01
Cresol is a prototype molecule in understanding intermolecular interactions in material and biological systems, because it offers different binding sites with various solvents and protonation states under different pH values. It is found that the UV/Vis absorption spectra of o -cresol in aromatic solvents (benzene, toluene) are characterized by a sharp peak, unlike the broad double-peaks in 11 non-aromatic solvents. Both molecular dynamics simulations and electronic structure calculations revealed the formation of intermolecular π-complexation between o -cresol and aromatic solvents. The thermal movements of solvent and solute molecules render the conformations of o -cresol changing between trans and cis isomers. The π-interaction makes the cis configuration a dominant isomer, hence leading to the single keen-edged UV/Vis absorption peak at approximately 283 nm. The free conformation changes between trans and cis in aqueous solution rationalize the broader absorption peaks in the range of 260-280 nm. The pH dependence of the UV/Vis absorption spectra in aqueous solutions is also rationalized by different protonation states of o -cresol. The explicit solvent model with long-ranged interactions is vital to describe the effects of π-complexation and electrostatic interaction on the UV/Vis absorption spectra of o -cresol in toluene and alkaline aqueous (pH > 10.3) solutions, respectively.
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Modelling of ceramide interactions with porous graphite carbon in non-aqueous liquid chromatography.
West, C; Cilpa, G; Gaudin, K; Chaminade, P; Lesellier, E
2005-09-16
Interactions of solutes on porous graphitic carbon (PGC) with non-aqueous mobile phases are studied by the linear solvation energy relationship (LSER). Studies have been carried out with eight binary mixtures composed of a weak solvent (acetonitrile or methanol) and a strong solvent (tetrahydrofuran, n-butanol, CH2Cl2, 1,1,2-trichloro-2,2,1-trifluoroethane). The systematic analysis of a set of test compounds was performed for each solvent mixture in isocratic mode (50:50). The results were compared to those obtained on PGC with hydro-organic liquids and supercritical fluids. They were then correlated with the observed retention behaviour of lipid compounds, more particularly ceramides.
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Protein-Style Dynamical Transition in a Non-Biological Polymer and a Non-Aqueous Solvent.
Mamontov, E; Sharma, V K; Borreguero, J M; Tyagi, M
2016-03-31
Temperature-dependent onset of apparent anharmonicity in the microscopic dynamics of hydrated proteins and other biomolecules has been known as protein dynamical transition for the last quarter of a century. Using neutron scattering and molecular dynamics simulation, techniques most often associated with protein dynamical transition studies, we have investigated the microscopic dynamics of one of the most common polymers, polystyrene, which was exposed to toluene vapor, mimicking the process of protein hydration from water vapor. Polystyrene with adsorbed toluene is an example of a solvent-solute system, which, unlike biopolymers, is anhydrous and lacks hydrogen bonding. Nevertheless, it exhibits the essential traits of the dynamical transition in biomolecules, such as a specific dependence of the microscopic dynamics of both solvent and host on the temperature and the amount of solvent adsorbed. We conclude that the protein dynamical transition is a manifestation of a universal solvent-solute dynamical relationship, which is not specific to either biomolecules as solute, or aqueous media as solvent, or even a particular type of interactions between solvent and solute.
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Preparation of hydrophobic organic aeorgels
Baumann, Theodore F.; Satcher, Jr., Joe H.; Gash, Alexander E.
2007-11-06
Synthetic methods for the preparation of hydrophobic organics aerogels. One method involves the sol-gel polymerization of 1,3-dimethoxybenzene or 1,3,5-trimethoxybenzene with formaldehyde in non-aqueous solvents. Using a procedure analogous to the preparation of resorcinol-formaldehyde (RF) aerogels, this approach generates wet gels that can be dried using either supercritical solvent extraction to generate the new organic aerogels or air dried to produce an xerogel. Other methods involve the sol-gel polymerization of 1,3,5 trihydroxy benzene (phloroglucinol) or 1,3 dihydroxy benzene (resorcinol) and various aldehydes in non-aqueous solvents. These methods use a procedure analogous to the one-step base and two-step base/acid catalyzed polycondensation of phloroglucinol and formaldehyde, but the base catalyst used is triethylamine. These methods can be applied to a variety of other sol-gel precursors and solvent systems. These hydrophobic organics aerogels have numerous application potentials in the field of material absorbers and water-proof insulation.
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Preparation of hydrophobic organic aeorgels
Baumann, Theodore F.; Satcher, Jr., Joe H.; Gash, Alexander E.
2004-10-19
Synthetic methods for the preparation of hydrophobic organics aerogels. One method involves the sol-gel polymerization of 1,3-dimethoxybenzene or 1,3,5-trimethoxybenzene with formaldehyde in non-aqueous solvents. Using a procedure analogous to the preparation of resorcinol-formaldehyde (RF) aerogels, this approach generates wet gels that can be dried using either supercritical solvent extraction to generate the new organic aerogels or air dried to produce an xerogel. Other methods involve the sol-gel polymerization of 1,3,5 trihydroxy benzene (phloroglucinol) or 1,3 dihydroxy benzene (resorcinol) and various aldehydes in non-aqueous solvents. These methods use a procedure analogous to the one-step base and two-step base/acid catalyzed polycondensation of phloroglucinol and formaldehyde, but the base catalyst used is triethylamine. These methods can be applied to a variety of other sol-gel precursors and solvent systems. These hydrophobic organics aerogels have numerous application potentials in the field of material absorbers and water-proof insulation.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Jerome, K.M.; Looney, B.B.; Accorsi, F.
1996-09-01
Soils and groundwater beneath an abandoned process sewer line in the A/M Area of the Savannah River Site (SRS) contain elevated levels of volatile organic compounds, specifically trichloroethylene (TCE) and tetrachloroethylene (PCE), two common chlorinated solvents. These compounds have low aqueous solubilities, thus when released to the subsurface in sufficient quantity, tend to exist as immiscible fluids or nonaqueous phase liquids (NAPLs). Because chlorinated solvents are also denser than water, they are referred to by the acronym DNAPLs, or dense non-aqueous phase liquids. Technologies targeted at the efficient characterization or removal of DNAPL are not currently proven. For example, mostmore » DNAPL studies rely on traditional soil and water sampling and the fortuitous observation of immiscible solvent. Once DNAPL is identified, soil excavation (which is only applicable to small contained spill sites) is the only proven cleanup method. New cleanup approaches based on destruction of DNAPL either in situ or ex situ have been proposed and tested at the pilot scale. The proposed demonstration, as described in this report will evaluate the applicability to DNAPL plumes of a technology proven for in situ destruction of light non-aqueous phase liquids (LNAPLs) such as oils.« less
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Excited-state dynamics of mononucleotides and DNA strands in a deep eutectic solvent.
Zhang, Yuyuan; de La Harpe, Kimberly; Hariharan, Mahesh; Kohler, Bern
2018-04-17
The photophysics of several mono- and oligonucleotides were investigated in a deep eutectic solvent for the first time. The solvent glyceline, prepared as a 1 : 2 mole ratio mixture of choline chloride and glycerol, was used to study excited-state deactivation in a non-aqueous solvent by the use of steady-state and time-resolved spectroscopy. DNA strands in glyceline retain the secondary structures that are present in aqueous solution to some degree, thus enabling a study of the effects of solvent properties on the excited states of stacked bases and stacked base pairs. The excited-state lifetime of the mononucleotide 5'-AMP in glyceline is 630 fs, or twice as long as in aqueous solution. Even slower relaxation is seen for 5'-TMP in glyceline, and a possible triplet state with a lifetime greater than 3 ns is observed. Circular dichroism spectra show that the single strand (dA)18 and the duplex d(AT)9·d(AT)9 adopt similar structures in glyceline and in aqueous solution. Despite having similar conformations in both solvents, femtosecond transient absorption experiments reveal striking changes in the dynamics. Excited-state decay and vibrational cooling generally take place more slowly in glyceline than in water. Additionally, the fraction of long-lived excited states in both oligonucleotide systems is lower in glyceline than in aqueous solution. For a DNA duplex, water is suggested to favor decay pathways involving intrastrand charge separation, while the deep eutectic solvent favors interstrand deactivation channels involving neutral species. Slower solvation dynamics in the viscous deep eutectic solvent may also play a role. These results demonstrate that the dynamics of excitations in stacked bases and stacked base pairs depend not only on conformation, but are also highly sensitive to the solvent.
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Iodination of insulin in aqueous and organic solvents
Massaglia, A.; Rosa, U.; Rialdi, G.; Rossi, C. A.
1969-01-01
1. The iodination of insulin was studied under various experimental conditions in aqueous media and in some organic solvents, by measuring separately the uptake of iodine by the four tyrosyl groups and the relative amounts of monoiodotyrosine and di-iodotyrosine that are formed. In aqueous media from pH1 to pH9 the iodination occurs predominantly on the tyrosyl groups of the A chain. Some organic solvents increase the iodine uptake of the B-chain tyrosyl groups. Their efficacy in promoting iodination of Tyr-B-16 and Tyr-B-26 is in the order: ethylene glycol and propylene glycol≃methanol and ethanol>dioxan>8m-urea. 2. It is suggested that each of the four tyrosyl groups in insulin has a different environment: Tyr-A-14 is fully exposed to the solvent; Tyr-A-19 is sterically influenced by the environmental structure, possibly by the vicinity of a disulphide interchain bond; Tyr-B-16 is embedded into a non-polar area whose stability is virtually independent of the molecular conformation; Tyr-B-26 is probably in a situation similar to Tyr-B-16 with the difference that its non-polar environment depends on the preservation of the native structure. PMID:5346365
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BIOENHANCED IN-WELL VAPOR STRIPPING TO TREAT TRICHLOROETHYLENE(TCE)
Removal of chlorinated solvent contaminants at their subsurface source is one of the most challenging problems for remediation of these prevalent contaminants. Here, the solvents are generally present as dense non-aqueous phase liquids (DNAPLs). The potential for applicatio...
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Non-aqueous liquid compositions comprising ion exchange polymers
Kim, Yu Seung; Lee, Kwan-Soo; Rockward, Tommy Q. T.
2013-03-12
Compositions, and methods of making thereof, comprising from about 1% to about 5% of a perfluorinated sulfonic acid ionomer or a hydrocarbon-based ionomer; and from about 95% to about 99% of a solvent, said solvent consisting essentially of a polyol; wherein said composition is substantially free of water and wherein said ionomer is uniformly dispersed in said solvent.
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Non-aqueous liquid compositions comprising ion exchange polymers
Kim, Yu Seung [Los Alamos, NM; Lee, Kwan-Soo [Blacksburg, VA; Rockward, Tommy Q. T. [Rio Rancho, NM
2011-07-19
Compositions, and methods of making thereof, comprising from about 1% to about 5% of a perfluorinated sulfonic acid ionomer or a hydrocarbon-based ionomer; and from about 95% to about 99% of a solvent, said solvent consisting essentially of a polyol; wherein said composition is substantially free of water and wherein said ionomer is uniformly dispersed in said solvent.
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NASA Astrophysics Data System (ADS)
Odinokov, A. V.; Leontyev, I. V.; Basilevsky, M. V.; Petrov, N. Ch.
2011-01-01
Potentials of mean force (PMF) are calculated for two model ion pairs in two non-aqueous solvents. Standard non-polarizable molecular dynamics simulation (NPMD) and approximate polarizable simulation (PMD) are implemented and compared as tools for monitoring PMF profiles. For the polar solvent (dimethylsulfoxide, DMSO) the PMF generated in terms of the NPMD reproduces fairly well the refined PMD-PMF profile. For the non-polar solvent (benzene) the conventional NPMD computation proves to be deficient. The validity of the correction found in terms of the approximate PMD approach is verified by its comparison with the result of the explicit PMD computation in benzene. The shapes of the PMF profiles in DMSO and in benzene are quite different. In DMSO, owing to dielectric screening, the PMF presents a flat plot with a shallow minimum positioned in the vicinity of the van der Waals contact of the ion pair. For the benzene case, the observed minimum proves to be unexpectedly deep, which manifests the formation of a tightly-binded contact ion pair. This remarkable effect arises owing to the strong electrostatic interaction that is incompletely screened by a non-polar medium. The PMFs for the binary benzene/DMSO mixtures display intermediate behaviour depending on the DMSO content.
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NASA Astrophysics Data System (ADS)
Bamgbopa, Musbaudeen O.; Almheiri, Saif
2017-02-01
The importance of the choice of solvent in a non-aqueous redox flow battery (NARFB) cannot be overemphasized. Several studies demonstrated the influence of the solvent on electrolyte performance in terms of reaction rates, energy/power densities, and efficiencies. In this work, we investigate capacity decay as a direct consequence of varying reactant crossover rates through membranes in different solvent environments. Specifically, we demonstrate the superiority of an 84/16 vol% acetonitrile/1,3 dioxolane solvent mixture over pure acetonitrile in terms of energy efficiency (up to 89%) and capacity retention for vanadium NARFBs - while incorporating a Nafion 115 membrane. The permeability of Nafion to the vanadium acetylacetonate active species is an order of magnitude lower when pure acetonitrile is replaced by the solvent mixture. A method to estimate relative membrane permeability is formulated from numerical analysis of self-discharge experimental data. Furthermore, tests on a modified Nafion/SiO2 membrane, which generally offered low species permeability, also show that different solvents alter membrane permeability. Elemental and morphological analyses of cycled Nafion and NafionSi membranes in different solvent environments indicate that different crossover rates induced by the choice of solvent during cycling are due to changes in the membrane microstructure, intrinsic permeability, swelling rates, and chemical stability.
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A microfluidic study of liquid-liquid extraction mediated by carbon dioxide.
Lestari, Gabriella; Salari, Alinaghi; Abolhasani, Milad; Kumacheva, Eugenia
2016-07-05
Liquid-liquid extraction is an important separation and purification method; however, it faces a challenge in reducing the energy consumption and the environmental impact of solvent (extractant) recovery. The reversible chemical reactions of switchable solvents (nitrogenous bases) with carbon dioxide (CO2) can be implemented in reactive liquid-liquid extraction to significantly reduce the cost and energy requirements of solvent recovery. The development of new effective switchable solvents reacting with CO2 and the optimization of extraction conditions rely on the ability to evaluate and screen the performance of switchable solvents in extraction processes. We report a microfluidic strategy for time- and labour-efficient studies of CO2-mediated solvent extraction. The platform utilizes a liquid segment containing an aqueous extractant droplet and a droplet of a solution of a switchable solvent in a non-polar liquid, with gaseous CO2 supplied to the segment from both sides. Following the reaction of the switchable solvent with CO2, the solvent becomes hydrophilic and transfers from the non-polar solvent to the aqueous droplet. By monitoring the time-dependent variation in droplet volumes, we determined the efficiency and extraction time for the CO2-mediated extraction of different nitrogenous bases in a broad experimental parameter space. The platform enables a significant reduction in the amount of switchable solvents used in these studies, provides accurate temporal characterization of the liquid-liquid extraction process, and offers the capability of high-throughput screening of switchable solvents.
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Jonke, A.A.
1957-10-01
In improved solvent extraction process is described for the extraction of metal values from highly dilute aqueous solutions. The process comprises contacting an aqueous solution with an organic substantially water-immiscible solvent, whereby metal values are taken up by a solvent extract phase; scrubbing the solvent extract phase with an aqueous scrubbing solution; separating an aqueous solution from the scrubbed solvent extract phase; and contacting the scrubbed solvent phase with an aqueous medium whereby the extracted metal values are removed from the solvent phase and taken up by said medium to form a strip solution containing said metal values, the aqueous scrubbing solution being a mixture of strip solution and an aqueous solution which contains mineral acids anions and is free of the metal values. The process is particularly effective for purifying uranium, where one starts with impure aqueous uranyl nitrate, extracts with tributyl phosphate dissolved in carbon tetrachloride, scrubs with aqueous nitric acid and employs water to strip the uranium from the scrubbed organic phase.
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Wang, Junmei; Hou, Tingjun
2011-01-01
In this work, we have evaluated how well the General AMBER force field (GAFF) performs in studying the dynamic properties of liquids. Diffusion coefficients (D) have been predicted for 17 solvents, 5 organic compounds in aqueous solutions, 4 proteins in aqueous solutions, and 9 organic compounds in non-aqueous solutions. An efficient sampling strategy has been proposed and tested in the calculation of the diffusion coefficients of solutes in solutions. There are two major findings of this study. First of all, the diffusion coefficients of organic solutes in aqueous solution can be well predicted: the average unsigned error (AUE) and the root-mean-square error (RMSE) are 0.137 and 0.171 ×10−5 cm−2s−1, respectively. Second, although the absolute values of D cannot be predicted, good correlations have been achieved for 8 organic solvents with experimental data (R2 = 0.784), 4 proteins in aqueous solutions (R2 = 0.996) and 9 organic compounds in non-aqueous solutions (R2 = 0.834). The temperature dependent behaviors of three solvents, namely, TIP3P water, dimethyl sulfoxide (DMSO) and cyclohexane have been studied. The major MD settings, such as the sizes of simulation boxes and with/without wrapping the coordinates of MD snapshots into the primary simulation boxes have been explored. We have concluded that our sampling strategy that averaging the mean square displacement (MSD) collected in multiple short-MD simulations is efficient in predicting diffusion coefficients of solutes at infinite dilution. PMID:21953689
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Non-aqueous liquid compositions comprising ion exchange polymers reference to related application
Kim,; Yu Seung, Lee [Los Alamos, NM; Kwan-Soo, Rockward [Los Alamos, NM; T, Tommy Q [Rio Rancho, NM
2012-08-07
Compositions, and methods of making thereof, comprising from about 1% to about 5% of a perfluorinated sulfonic acid ionomer or a hydrocarbon-based ionomer; and from about 95% to about 99% of a solvent, said solvent consisting essentially of a polyol; wherein said composition is substantially free of water and wherein said ionomer is uniformly dispersed in said solvent.
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NASA Astrophysics Data System (ADS)
Gunceler, Deniz
Solvents are of great importance in many technological applications, but are difficult to study using standard, off-the-shelf ab initio electronic structure methods. This is because a single configuration of molecular positions in the solvent (a "snapshot" of the fluid) is not necessarily representative of the thermodynamic average. To obtain any thermodynamic averages (e.g. free energies), the phase space of the solvent must be sampled, typically using molecular dynamics. This greatly increases the computational cost involved in studying solvated systems. Joint density-functional theory has made its mark by being a computationally efficient yet rigorous theory by which to study solvation. It replaces the need for thermodynamic sampling with an effective continuum description of the solvent environment that is in-principle exact, computationally efficient and intuitive (easier to interpret). It has been very successful in aqueous systems, with potential applications in (among others) energy materials discovery, catalysis and surface science. In this dissertation, we develop accurate and fast joint density functional theories for complex, non-aqueous solvent enviroments, including organic solvents and room temperature ionic liquids, as well as new methods for calculating electron excitation spectra in such systems. These theories are then applied to a range of physical problems, from dendrite formation in lithium-metal batteries to the optical spectra of solvated ions.
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Gao, Wenyuan; Fan, Haiyang; Chen, Lifeng; Wang, Hualei; Wei, Dongzhi
2016-07-01
To identify an esterase-mediated kinetic resolution of secondary alcohols in non-aqueous medium. An esterase, EST4, from a marine mud metagenomic library, showed high activity and enantioselectivity for the kinetic resolution of secondary alcohols in non-aqueous medium. Using 1-phenylethanol as the model alcohol, the effects of organic solvents, acyl donors, molar ratio, temperatures and biocatalyst loading on the kinetic resolution catalyzed by the EST4 whole-cell biocatalyst were investigated and optimized. The optimized methodology was effective on resolving 16 various racemic secondary alcohols in neat n-hexane, providing excellent enantiomeric excess (up to 99.9 % ee). Moreover, EST4 exhibited a strong tolerance for high substrate concentration (up to 1 M), and the optical purity of the desired secondary alcohols was kept above 99 % ee. The esterase EST4 is a promising biocatalyst for the enantioselective synthesis of various alcohols and esters with interesting practical applications.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Hancu, Dan
GE Global Research has developed, over the last 8 years, a platform of cost effective CO2 capture technologies based on a non-aqueous aminosilicone solvent (GAP-1m). As demonstrated in previous funded DOE projects (DE-FE0007502 and DEFE0013755), the GAP-1m solvent has increased CO2 working capacity, lower volatility and corrosivity than the benchmark aqueous amine technology. Performance of the GAP-1m solvent was recently demonstrated in a 0.5 MWe pilot at National Carbon Capture Center, AL with real flue gas for over 500 hours of operation using a Steam Stripper Column (SSC). The pilot-scale PSTU engineering data were used to (i) update the techno-economicmore » analysis, and EH&S assessment, (ii) perform technology gap analysis, and (iii) conduct the solvent manufacturability and scale-up study.« less
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Dispersions of Goethite Nanorods in Aprotic Polar Solvents
Coursault, Delphine; Dozov, Ivan; Nobili, Maurizio; Dupont, Laurent; Chanéac, Corinne
2017-01-01
Colloidal suspensions of anisotropic nanoparticles can spontaneously self-organize in liquid-crystalline phases beyond some concentration threshold. These phases often respond to electric and magnetic fields. At lower concentrations, usual isotropic liquids are observed but they can display very strong Kerr and Cotton-Mouton effects (i.e., field-induced particle orientation). For many examples of these colloidal suspensions, the solvent is water, which hinders most electro-optic applications. Here, for goethite (α-FeOOH) nanorod dispersions, we show that water can be replaced by polar aprotic solvents, such as N-methyl-2-pyrrolidone (NMP) and dimethylsulfoxide (DMSO), without loss of colloidal stability. By polarized-light microscopy, small-angle X-ray scattering and electro-optic measurements, we found that the nematic phase, with its field-response properties, is retained. Moreover, a strong Kerr effect was also observed with isotropic goethite suspensions in these polar aprotic solvents. Furthermore, we found no significant difference in the behavior of both the nematic and isotropic phases between the aqueous and non-aqueous dispersions. Our work shows that goethite nanorod suspensions in polar aprotic solvents, suitable for electro-optic applications, can easily be produced and that they keep all their outstanding properties. It also suggests that this solvent replacement method could be extended to the aqueous colloidal suspensions of other kinds of charged anisotropic nanoparticles. PMID:29039797
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Cantu, David C.; Malhotra, Deepika; Koech, Phillip K.
2016-01-01
CO2 capture from power generation with aqueous solvents remains energy intensive due to the high water content of the current technology, or the high viscosity of non-aqueous alternatives. Quantitative reduced models, connecting molecular structure to bulk properties, are key for developing structure-property relationships that enable molecular design. In this work, we describe such a model that quantitatively predicts viscosities of CO2 binding organic liquids (CO2BOLs) based solely on molecular structure and the amount of bound CO2. The functional form of the model correlates the viscosity with the CO2 loading and an electrostatic term describing the charge distribution between the CO2-bearingmore » functional group and the proton-receiving amine. Molecular simulations identify the proton shuttle between these groups within the same molecule to be the critical indicator of low viscosity. The model, developed to allow for quick screening of solvent libraries, paves the way towards the rational design of low viscosity non-aqueous solvent systems for post-combustion CO2 capture. Following these theoretical recommendations, synthetic efforts of promising candidates and viscosity measurement provide experimental validation and verification.« less
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Ward, Keeran; Xi, Jingshu; Stuckey, David C
2015-12-01
The use of non-ionic colloidal liquid aphrons (CLAs) as a support for enzyme immobilisation was investigated. Formulation required the mixing of an aqueous-surfactant solution with a relatively non-polar solvent-surfactant solution, forming a solvent droplet surrounded by a thin stabilised aqueous film (soapy shell). Studies utilising anionic surfactants have showed increased retention, however, very little have been understood about the forces governing immobilisation. This study seeks to determine the effects of enzyme properties on CLA immobilisation by examining a non-ionic/non-polar solvent system comprised of two non-ionic surfactants, Tween 20 and 80, mineral oil and the enzymes lipase, aprotinin and α-chymotrypsin. From these results it was deduced that hydrophobic interactions strongly governed immobilisation. Confocal Scanning Laser Microscopy (CSLM) revealed that immobilisation was predominantly achieved by surface adsorption attributed to hydrophobic interactions between the enzyme and the CLA surface. Enzyme surface affinity was found to increase when added directly to the formulation (pre-manufacture addition), as opposed to the bulk continuous phase (post-manufacture addition), with α-chymotrypsin and aprotinin being the most perturbed, while lipase was relatively unaffected. The effect of zeta potential on immobilisation showed that enzymes adsorbed better closer to their pI, indicating that charge minimisation was necessary for immobilisation. Finally, the effect of increasing enzyme concentration in the aqueous phase resulted in an increase in adsorption for all enzymes due to cooperativity between protein molecules, with saturation occurring faster at higher adsorption rates. Copyright © 2015 Elsevier B.V. All rights reserved.
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Kenndler, Ernst
2014-03-28
This two-part review critically gives an overview on the theoretical and practical advances in non-aqueous capillary electrophoresis (NACE) achieved over the recent five years. Part I starts out by reviewing the aspects relevant to electromigration in organic solvents and evaluates potential advantages of the latter in comparison to aqueous solvent systems. The crucial role of solubility for the species involved in CE - analytes and back ground electrolyte constituents - is discussed both for ionic and neutral compounds. The impact of organic solvents on the electrophoretic and electroosmotic mobility and on the ionization (pKa values) of weak acids and bases is highlighted. Special emphasis is placed on methanol, acetonitrile and mixtures of these solvents, being the most frequent employed media for NACE applications. In addition, also solvents less commonly used in NACE will be covered, including other alcohols, amides (formamide, N-methylformamide, N,N-dimethylformamide, N,N-dimethylacetamide), propylene carbonate, dimethylsulphoxide, and nitromethane. The discussions address the consequences of dramatic pKa shifts frequently seen for weak acids and bases, and the important contributions of medium-specific electroosmotic flow (EOF) to electromigration in nonaqueous media. Important for NACE, the role of the water content on pKa and mobility is analyzed. Finally, association phenomena rather specific to nonaqueous solvents (ion pairing, homo- and heteroconjugation) will be addressed, along with their potential advantages for the development of NACE separation protocols. It is pointed out that this review is not intended as a listing of all papers that have been published on NACE in the period mentioned above. It rather deals with general aspects of migration and selectivity in organic solvent systems, and discusses - critically - examples from the literature with particular interest to the topic. An analog discussion about the role of the solvent on efficiency will be presented in Part II. Copyright © 2014 Elsevier B.V. All rights reserved.
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NASA Astrophysics Data System (ADS)
Habibi, N.; Rounaghi, G. H.; Mohajeri, M.
2012-12-01
The complexation reaction of macrocyclic ligand (4'-nitrobenzo-15C5) with Y3+ cation was studied in acetonitrile-methanol (AN-MeOH), acetonitrile-ethanol (AN-EtOH), acetonitrile-dimethylformamide (AN-DMF) and ethylacetate-methanol (EtOAc-MeOH) binary mixtures at different temperatures using conductometry method. The conductivity data show that in all solvent systems, the stoichiometry of the complex formed between 4'-nitrobenzo-15C5 and Y3+ cation is 1: 1 (ML). The stability order of (4'-nitrobenzo-15C5). Y3+ complex in pure non-aqueous solvents at 25°C was found to be: EtOAc > EtOH > AN ≈ DMF > MeOH, and in the case of most compositions of the binary mixed solvents at 25°C it was: AN≈MeOH ≈ AN-EtOH > AN-DMF > EtOAc-MeOH. But the results indicate that the sequence of the stability of the complex in the binary mixed solutions changes with temperature. A non-linear behavior was observed for changes of log K f of (4'-nitrobenzo-15C5 · Y3+) complex versus the composition of the binary mixed solvents, which was explained in terms of solvent-solvent interactions and also the hetero-selective solvation of the species involved in the complexation reaction. The values of thermodynamic parameters (Δ H {c/ℴ} and Δ S {c/ℴ}) for formation of the complex were obtained from temperature dependent of the stability constant using the van't Hoff plots. The results represent that in most cases, the complex is both enthalpy and entropy stabilized and the values and also the sign of thermodynamic parameters are influenced by the nature and composition of the mixed solvents.
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Kim, Daejin; Powell, Lawrence E; Delmau, Lætitia H; Peterson, Eric S; Herchenroeder, Jim; Bhave, Ramesh R
2015-08-18
The rare earth elements (REEs) such as neodymium, praseodymium, and dysprosium were successfully recovered from commercial NdFeB magnets and industrial scrap magnets via membrane assisted solvent extraction (MSX). A hollow fiber membrane system was evaluated to extract REEs in a single step with the feed and strip solutions circulating continuously through the MSX system. The effects of several experimental variables on REE extraction such as flow rate, concentration of REEs in the feed solution, membrane configuration, and composition of acids were investigated with the MSX system. A multimembrane module configuration with REEs dissolved in aqueous nitric acid solutions showed high selectivity for REE extraction with no coextraction of non-REEs, whereas the use of aqueous hydrochloric acid solution resulted in coextraction of non-REEs due to the formation of chloroanions of non-REEs. The REE oxides were recovered from the strip solution through precipitation, drying, and annealing steps. The resulting REE oxides were characterized with XRD, SEM-EDX, and ICP-OES, demonstrating that the membrane assisted solvent extraction is capable of selectively recovering pure REEs from the industrial scrap magnets.
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NASA Astrophysics Data System (ADS)
Hailegiorgis, Sintayehu Mekuria; Khan, Saleem Nawaz; Abdolah, Nur Hanis H.; Ayoub, Muhammad; Tesfamichael, Aklilu
2017-10-01
In this study, aqueous hybrid solvents from a mixture of aqueous N-methyldiethanolamine (MDEA) and 1-butyl-3-methylimidazolium acetate, [bmim][Ac] as ionic liquids (ILs) were formulated at different mass ratio. In each aqueous hybrid solvents, the concentrations of MDEA were kept constant at 30 wt%. In the hybrid solvents, the solubility of CO2 was investigated at [bmim][Ac] concentration of 10 wt% and 20 wt%, respectively and results were compared with pure aqueous MDEA solvent. It was observed that the solubility of CO2 is significantly improved in the hybrid solvent as compared to the solubility of CO2 in pure aqueous MDEA solvent. However, increasing the concentration of [bmim][Ac] from 10 wt% to 20 wt% has a negative effect on the solubility of CO2 due to viscosity effect. It was also observed that hybrid solvents with 10 wt% [bmim][Ac] has better CO2 loading capacity. Increasing pressure from 10 bar to 20 bar has demonstrated an increase in CO2 absorption capacity as well as CO2 absorption rate. Hybrid solvents prepared from amine and imidazolium ILs will be a promising solvent in the capturing of CO2.
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Organic non-aqueous cation-based redox flow batteries
DOE Office of Scientific and Technical Information (OSTI.GOV)
Zhang, Lu; Huang, Jinhua; Burrell, Anthony
The present invention provides a non-aqueous redox flow battery comprising a negative electrode immersed in a non-aqueous liquid negative electrolyte, a positive electrode immersed in a non-aqueous liquid positive electrolyte, and a cation-permeable separator (e.g., a porous membrane, film, sheet, or panel) between the negative electrolyte from the positive electrolyte. During charging and discharging, the electrolytes are circulated over their respective electrodes. The electrolytes each comprise an electrolyte salt (e.g., a lithium or sodium salt), a transition-metal free redox reactant, and optionally an electrochemically stable organic solvent. Each redox reactant is selected from an organic compound comprising a conjugated unsaturatedmore » moiety, a boron cluster compound, and a combination thereof. The organic redox reactant of the positive electrolyte comprises a tetrafluorohydroquinone ether compound or a tetrafluorocatechol ether compound.« less
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Shukla, Shashi Kant; Pandey, Shubha; Pandey, Siddharth
2018-07-20
Ionic liquids (ILs) have been receiving much attention in many fields of analytical chemistry because of their various interesting properties which distinguish them from volatile organic compounds. They offer both directional and non-directional forces towards a solute molecule and therefore act as excellent solvents for a wide range of polar and non-polar compounds. Because of the presence of various possible interactions, ILs easily undergo biphasic separation with water and other less polar/non-polar organic solvents. Their ability to create biphasic splitting makes them a promising candidate for liquid-liquid separation processes, such as aqueous biphasic systems and liquid-liquid equilibria. Various aspects of ILs in these separation methods are discussed in view of the origin of physical forces responsible for the biphasic interactions, the effect of structural components, temperature, pressure, pH and additives. The specific advantages of using ILs in aqueous biphasic systems and liquid-liquid equilibria in binary and ternary systems are discussed with a view to defining their future role in separation processes by giving major emphasis on developing non-toxic ILs with physical and solution properties tailored to the needs of specific sample preparation techniques. Copyright © 2017 Elsevier B.V. All rights reserved.
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Magnesium Electrorefining in Non-Aqueous Electrolyte at Room Temperature
NASA Astrophysics Data System (ADS)
Kwon, Kyungjung; Park, Jesik; Kusumah, Priyandi; Dilasari, Bonita; Kim, Hansu; Lee, Churl Kyoung
Magnesium, of which application is often limited by its poor corrosion resistance, is more vulnerable to corrosion with existence of metal impurities such as Fe. Therefore, for the refining and recycling of magnesium, high temperature electrolysis using molten salts has been frequently adopted. In this report, the purification of magnesium scrap by electrolysis at room temperature is investigated with non-aqueous electrolytes. An aprotic solvent of tetrahydrofuran (THF) was used as a solvent of the electrolyte. Magnesium scrap was used as anode materials and ethyl magnesium bromide (EtMgBr) was dissolved in THF for magnesium source. The purified magnesium can be uniformly electrodeposited on copper electrode under potentiostatic conditions. The deposits were confirmed by scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDS) analysis.
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Steinle, Dominik; Friedrich, Laura; Bevilacqua, Nico; von Hauff, Elizabeth; Gschwind, Fabienne
2016-01-01
One of the problems that arise with bifluoride- or fluoride-containing compounds is their poor solubility in non-aqueous solvents. We report herein a facile one-pot synthesis and the chemical analysis of fluoride/bifluoride-containing polymers, which are soluble in MeCN. Different polymers, such as Polyvinylacetate or Polyethylene imine and saccharides, such as maltodextrin, were complexed with ammonium (bi)fluoride using hydrogen bonds to form the desired (bi)fluoride-containing compounds. The newly formed hydrogen bonding (bi)fluoride-doped polymer matrices were analyzed using infrared and nuclear magnetic resonance spectroscopies, and X-ray diffraction. The promising materials also underwent impedance spectroscopy, conductivity measurements and preliminary tests as electrolytes for room temperature fluoride ion batteries along with an analysis of their performance. PMID:28774092
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Chung, Y L; Liu, J T; Lin, C H
2001-08-15
The analytical profiles for 3,4-methylenedioxymethamphetamine (3,4-MDMA) and related amphetamines in urine samples are described for non-aqueous capillary electrophoresis-fluorescence spectroscopy. 3,4-MDMA was detected and identified on-line, using a cryogenic molecular fluorescence technique at 77 K. Under optimized conditions, baseline separation of the selected compounds was achieved in less than 12 min. Precision was evaluated by measuring the repeatability and intermediate precision of the migration times and corrected peak areas. The non-aqueous CE separation conditions and the spectral characteristics of 3,4-MDMA with respect to solvent and temperature effects are also discussed.
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Wijaya, Emmy C; Separovic, Frances; Drummond, Calum J; Greaves, Tamar L
2016-09-21
Improving protein stabilisation is important for the further development of many applications in the pharmaceutical, specialty chemical, consumer product and agricultural sectors. However, protein stabilization is highly dependent on the solvent environment and, hence, it is very complex to tailor protein-solvent combinations for stable protein maintenance. Understanding solvent features that govern protein stabilization will enable selection or design of suitable media with favourable solution environments to retain protein native conformation. In this work the structural conformation and activity of lysozyme in 29 solvent systems were investigated to determine the role of various solvent features on the stability of the enzyme. The solvent systems consisted of 19 low molecular weight polar solvents and 4 protic ionic liquids (PILs), both at different water content levels, and 6 aqueous salt solutions. Small angle X-ray scattering, Fourier transform infrared spectroscopy and UV-vis spectroscopy were used to investigate the tertiary and secondary structure of lysozyme along with the corresponding activity in various solvation systems. At low non-aqueous solvent concentrations (high water content), the presence of solvents and salts generally maintained lysozyme in its native structure and enhanced its activity. Due to the presence of a net surface charge on lysozyme, electrostatic interactions in PIL-water systems and salt solutions enhanced lysozyme activity more than the specific hydrogen-bond interactions present in non-ionic molecular solvents. At higher solvent concentrations (lower water content), solvents with a propensity to exhibit the solvophobic effect, analogous to the hydrophobic effect in water, retained lysozyme native conformation and activity. This solvophobic effect was observed particularly for solvents which contained hydroxyl moieties. Preferential solvophobic effects along with bulky chemical structures were postulated to result in less competition with water at the specific hydration layer around the protein, thus reducing protein-solvent interactions and retaining lysozyme's native conformation. The structure-property links established in this study are considered to be applicable to other proteins.
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Lid dynamics of porcine pancreatic lipase in non-aqueous solvents.
Haque, Neshatul; Prabhu, N Prakash
2016-10-01
Understanding the dynamics of enzymes in organic solvents has wider implications on their industrial applications. Pancreatic lipases, which show activity in their lid open-state, demonstrate enhanced activity in organic solvents at higher temperatures. However, the lid dynamics of pancreatic lipases in non-aqueous environment is yet to be clearly understood. Dynamics of porcine pancreatic lipase (PPL) in open and closed conformations was followed in ethanol, toluene, and octanol using molecular simulation methods. In silico double mutant D250V and E254L of PPL (PPLmut-Cl) was created and its lid opening dynamics in water and in octanol was analyzed. PPL showed increase in solvent accessible surface area and decrease in packing density as the polarity of the surrounded solvent decreased. Breaking the interactions between D250-Y115, and D250-E254 in PPLmut-Cl directed the lid to attain open-state conformation. Major energy barriers during the lid movement in water and in octanol were identified. Also, the trajectories of lid movement were found to be different in these solvents. Only the double mutant at higher temperature showed lid opening movement suggesting the essential role of the three residues in holding the lid in closed conformation. The lid opening dynamics was faster in octanol than water suggesting that non-polar solvents favor open conformation of the lid. This study identifies important interactions between the lid and the residues in domain 1 which possibly keeps the lid in closed conformation. Also, it explains the rearrangements of residue-residue interactions during lid opening movement in water and in octanol. Copyright © 2016 Elsevier B.V. All rights reserved.
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McBride, Devin W.; Rodgers, Victor G. J.
2013-01-01
The activity coefficient is largely considered an empirical parameter that was traditionally introduced to correct the non-ideality observed in thermodynamic systems such as osmotic pressure. Here, the activity coefficient of free-solvent is related to physically realistic parameters and a mathematical expression is developed to directly predict the activity coefficients of free-solvent, for aqueous protein solutions up to near-saturation concentrations. The model is based on the free-solvent model, which has previously been shown to provide excellent prediction of the osmotic pressure of concentrated and crowded globular proteins in aqueous solutions up to near-saturation concentrations. Thus, this model uses only the independently determined, physically realizable quantities: mole fraction, solvent accessible surface area, and ion binding, in its prediction. Predictions are presented for the activity coefficients of free-solvent for near-saturated protein solutions containing either bovine serum albumin or hemoglobin. As a verification step, the predictability of the model for the activity coefficient of sucrose solutions was evaluated. The predicted activity coefficients of free-solvent are compared to the calculated activity coefficients of free-solvent based on osmotic pressure data. It is observed that the predicted activity coefficients are increasingly dependent on the solute-solvent parameters as the protein concentration increases to near-saturation concentrations. PMID:24324733
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NASA Astrophysics Data System (ADS)
Smirnov, V. I.; Badelin, V. G.
2018-01-01
The enthalpies of solution of 4-hydroxy-L-proline and L-phenylalanine in binary mixed aqueous solvents containing acetonitrile (AN), 1,4-dioxane (1,4-DO), or acetone (AC) at mole fractions of 0 to 0.25 are determined at T = 298.15 K via isothermal calorimetry. The standard enthalpies of solution (Δsol H°) and transfer (Δtr H°) of 4-hydroxy-L-proline and L-phenylalanine from water to mixed aqueous solvents are calculated using the experimental calorimetric data, as are the enthalpy coefficients of paired interactions ( h xy ) between the molecules of the investigated amino acids and the organic solvents. The effects the mixed aqueous solvent composition and the structure of the organic solvent molecules have on the enthalpies of solution and transfer for the investigated amino acids are considered. The correlation between the enthalpy of solution of the amino acids and the electron-donating properties of the organic solvents in the mixed aqueous solvent systems is established.
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A theoretical study of the effect of a non-aqueous proton donor on electrochemical ammonia synthesis
Zhang, Linan; Mallikarjun Sharada, Shaama; Singh, Aayush R.; ...
2018-01-17
We report that ammonia synthesis is one of the most studied reactions in heterogeneous catalysis. To date, however, electrochemical N 2 reduction in aqueous systems has proven to be extremely difficult, mainly due to the competing hydrogen evolution reaction (HER). Recently, it has been shown that transition metal complexes based on molybdenum can reduce N 2 to ammonia at room temperature and ambient pressure in a non-aqueous system, with a relatively small amount of hydrogen output. We demonstrate that the non-aqueous proton donor they have chosen, 2,6-lutidinium (LutH +), is a viable substitute for hydronium in the electrochemical process atmore » a solid surface, since this donor can suppress the HER rate. Finally, we also show that the presence of LutH + can selectively stabilize the *NNH intermediate relative to *NH or *NH 2via the formation of hydrogen bonds, indicating that the use of non-aqueous solvents can break the scaling relationship between limiting potential and binding energies.« less
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A theoretical study of the effect of a non-aqueous proton donor on electrochemical ammonia synthesis
DOE Office of Scientific and Technical Information (OSTI.GOV)
Zhang, Linan; Mallikarjun Sharada, Shaama; Singh, Aayush R.
We report that ammonia synthesis is one of the most studied reactions in heterogeneous catalysis. To date, however, electrochemical N 2 reduction in aqueous systems has proven to be extremely difficult, mainly due to the competing hydrogen evolution reaction (HER). Recently, it has been shown that transition metal complexes based on molybdenum can reduce N 2 to ammonia at room temperature and ambient pressure in a non-aqueous system, with a relatively small amount of hydrogen output. We demonstrate that the non-aqueous proton donor they have chosen, 2,6-lutidinium (LutH +), is a viable substitute for hydronium in the electrochemical process atmore » a solid surface, since this donor can suppress the HER rate. Finally, we also show that the presence of LutH + can selectively stabilize the *NNH intermediate relative to *NH or *NH 2via the formation of hydrogen bonds, indicating that the use of non-aqueous solvents can break the scaling relationship between limiting potential and binding energies.« less
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Micro-Encapsulation of non-aqueous solvents for energy-efficient carbon capture
DOE Office of Scientific and Technical Information (OSTI.GOV)
Stolaroff, Joshua K; Ye, Congwang; Oakdale, James
Here, we demonstrate micro-encapsulation of several promising designer solvents: an IL, PCIL, and CO2BOL. We develop custom polymers that cure by UV light in the presence of each solvent while maintaining high CO2 permeability. We use several new process strategies to accommodate the viscosity and phase changes. We then measure and compare the CO2 absorption rate and capacity as well as the multi-cycle performance of the encapsulated solvents. These results are compared with previous work on encapsulated sodium carbonate solution. The prospects for designer solvents to reduce the cost of post-combustion capture and the implications for process design with encapsulatedmore » solvents are discussed.« less
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Kim, Daejin; Powell, Lawrence E.; Delmau, Lætitia H.; ...
2015-06-24
In this paper, the rare earth elements (REEs) such as neodymium, praseodymium, and dysprosium were successfully recovered from commercial NdFeB magnets and industrial scrap magnets via membrane assisted solvent extraction (MSX). A hollow fiber membrane system was evaluated to extract REEs in a single step with the feed and strip solutions circulating continuously through the MSX system. The effects of several experimental variables on REE extraction such as flow rate, concentration of REEs in the feed solution, membrane configuration, and composition of acids were investigated with the MSX system. A multimembrane module configuration with REEs dissolved in aqueous nitric acidmore » solutions showed high selectivity for REE extraction with no coextraction of non-REEs, whereas the use of aqueous hydrochloric acid solution resulted in coextraction of non-REEs due to the formation of chloroanions of non-REEs. The REE oxides were recovered from the strip solution through precipitation, drying, and annealing steps. Finally, the resulting REE oxides were characterized with XRD, SEM-EDX, and ICP-OES, demonstrating that the membrane assisted solvent extraction is capable of selectively recovering pure REEs from the industrial scrap magnets.« less
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Method of remediation of contaminants in porous media through minimization of bouyancy effects
Shook, G. Michael; Pope, Gary A.
1999-01-01
A method for controlling vertical migration of contaminants in an aquifer includes introduction of a solubilizing solution having a surfactant and an alcohol or other light co-solvent. The surfactant is selected to solubilize the contaminant. The alcohol or other solvent is selected to provide the microemulsion with a substantially neutral buoyancy with respect to groundwater. The neutral buoyancy of the microemulsion prevents the normal downward movement which is typical of the solubilized dense non-aqueous phase liquid in surfactant-enhanced aquifer remediation. Thus, the risk that any significant amount of the solubilized dense non-aqueous contaminants will migrate vertically can be controlled. The relative tendency for vertical migration may also be reduced by increasing the injection rate or injected fluid viscosity (by adding polymer), or by reducing the well spacing.
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PROCESS OF SEPARATING URANIUM FROM AQUEOUS SOLUTION BY SOLVENT EXTRACTION
Warf, J.C.
1958-08-19
A process is described for separating uranium values from aqueous uranyl nitrate solutions. The process consists in contacting the uramium bearing solution with an organic solvent, tributyl phosphate, preferably diluted with a less viscous organic liquida whereby the uranyl nitrate is extracted into the organic solvent phase. The uranvl nitrate may be recovered from the solvent phase bv back extracting with an aqueous mediuin.
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DNA Architectures for Templated Material Growth
2011-09-01
Solubilization of the DNA in non-aqueous solvents is achieved by replacing charge stabilizing salts with surfactants. Retention of DNA hierarchical structure...solvents is achieved by replacing charge stabilizing salts with surfactants. Retention of DNA hierarchical structure under both conditions will be...studied and explained, and is only being reproduced in this experiment.12-14 Both CTAB and CTAC, were reacted with the reconstituted DNA (salmon sperm
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Electric current-producing device having sulfone-based electrolyte
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.
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Gu, Minjeong; Cho, Keunchang; Kang, Seong Ho
2018-07-27
The migration behavior of organic fluorescent dyes (i.e., crystal violet, methyl violet base, methyl violet B base, rhodamine 6G, and rhodamine B base) in non-aqueous capillary electrophoresis (NACE) was investigated by focusing on the physicochemical properties of various organic solvents [ethanol, methanol, 2-propanol, dimethylformamide (DMF), and dimethyl sulfoxide (DMSO)] in background electrolyte (BGE). Laser-induced fluorescence (LIF) and UV/Vis detectors were employed to observe both the migration time of organic dyes and the electroosmotic flow (EOF) in NACE, respectively. As seen in conventional aqueous BGE, the mobility of EOF in organic solvents tended to rise when the ratio between the dielectric constant and the solvent's viscosity (ε/η) increased in accordance with Smoluchowski's equation. However, unlike the ε/η of pure organic solvents, the migration order of dyes changed as follows: methanol (60.0) > DMF (45.8) > ethanol (22.8) > DMSO (23.4) > 2-propanol (9.8). Since the amount of acetic acid added to balance the pH depends on the pK a of each solvent, EOF changed when the difference in the ε/η value was small. This resulted from the inhibition of mobility, and its difference was dependent on the ε/η of BGEs with high ionic strength. In particular, the actual mobility of dyes in DMF showed excellent compliance with the Debye-Hückel-Onsager (DHO) theory extended by Falkenhagen and Pitts, which enabled us to analyze all dyes within 15 min with excellent resolution (R s > 2.5) under optimum NACE conditions (10 mM sodium borate and 4661 mM acetic acid in 100% DMF, pH 4.5). In addition, the NACE method was successfully applied for analyzing commercially available ballpoint ink pens. Thus, these results could be used to anticipate the migration order of organic dyes in a 100% NACE separation system. Copyright © 2018 Elsevier B.V. All rights reserved.
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NASA Astrophysics Data System (ADS)
Lee, Youngme; Sah, Eric; Sah, Hongkee
2015-11-01
The objective of this study was to develop a new oil-in-water emulsion-based nanoencapsulation method for the preparation of PLGA nanoparticles using a non-halogenated solvent. PLGA (60-150 mg) was dissolved in 3 ml of methyl propionate, which was vortexed with 4 ml of a 0.5-4 % polyvinyl alcohol solution. This premix was sonicated for 2 min, added into 30 ml of the aqueous polyvinyl alcohol solution, and reacted with 3 ml of 10 N NaOH. Solvent removal was achieved by the alkaline hydrolysis of methyl propionate dissolved in an aqueous phase into water-soluble methanol and sodium propionate. It was a simple but effective technique to quickly harden nanoemulsion droplets into nanoparticles. The appearing PLGA nanoparticles were recovered by ultracentrifugation and/or dialysis, lyophilized with trehalose, and redispersed by water. This nanoencapsulation technique permitted a control of their mean diameters over 151.7 ± 3.8 to 440.2 ± 22.2 nm at mild processing conditions. When the aqueous polyvinyl alcohol concentration was set at ≥1 %, nanoparticles showed uniform distributions with polydispersity indices below 0.1. There were no significant changes in their mean diameters and size distribution patterns before and after lyophilization. When mestranol was encapsulated into nanoparticles, the drug was completely nanoencapsulated: depending on experimental conditions, their encapsulation efficiencies were determined to be 99.4 ± 7.2 to 105.8 ± 6.3 %. This simple, facile nanoencapsulation technique might have versatile applications for the preparation of polymeric nanoparticulate dosage forms.
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Solvent for urethane adhesives and coatings and method of use
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.
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Snitsarev, Vladislav; Young, Michael N; Miller, Ross M S; Rotella, David P
2013-01-01
(-)-Epigallocatechin 3-O-gallate (EGCG) a molecule found in green tea and known for a plethora of bioactive properties is an inhibitor of heat shock protein 90 (HSP90), a protein of interest as a target for cancer and neuroprotection. Determination of the spectral properties of EGCG fluorescence in environments similar to those of binding sites found in proteins provides an important tool to directly study protein-EGCG interactions. The goal of this study is to examine the spectral properties of EGCG fluorescence in an aqueous buffer (AB) at pH=7.0, acetonitrile (AN) (a polar aprotic solvent), dimethylsulfoxide (DMSO) (a polar aprotic solvent), and ethanol (EtOH) (a polar protic solvent). We demonstrate that EGCG is a highly fluorescent molecule when excited at approximately 275 nm with emission maxima between 350 and 400 nm depending on solvent. Another smaller excitation peak was found when EGCG is excited at approximately 235 nm with maximum emission between 340 and 400 nm. We found that the fluorescence intensity (FI) of EGCG in AB at pH=7.0 is significantly quenched, and that it is about 85 times higher in an aprotic solvent DMSO. The Stokes shifts of EGCG fluorescence were determined by solvent polarity. In addition, while the emission maxima of EGCG fluorescence in AB, DMSO, and EtOH follow the Lippert-Mataga equation, its fluorescence in AN points to non-specific solvent effects on EGCG fluorescence. We conclude that significant solvent-dependent changes in both fluorescence intensity and fluorescence emission shifts can be effectively used to distinguish EGCG in aqueous solutions from EGCG in environments of different polarity, and, thus, can be used to study specific EGCG binding to protein binding sites where the environment is often different from aqueous in terms of polarity.
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Biocatalytic transformations in ionic liquids.
van Rantwijk, Fred; Madeira Lau, Rute; Sheldon, Roger A
2003-03-01
Room temperature ionic liquids are non-volatile, thermally stable and highly polar; they are also moderately hydrophilic solvents. Here, we discuss their use as reaction media for biocatalysis. Enzymes of widely diverging types are catalytically active in ionic liquids or aqueous biphasic ionic liquid systems. Lipases, in particular, maintain their activity in anhydrous ionic liquid media; the (enantio)selectivity and operational stability are often better than in traditional media. The unconventional solvent properties of ionic liquids have been exploited in biocatalyst recycling and product recovery schemes that are not feasible with traditional solvent systems.
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Non-aqueous electrolytes for lithium ion batteries
Chen, Zonghai; Amine, Khalil
2015-11-12
The present invention is generally related to electrolytes containing anion receptor additives to enhance the power capability of lithium-ion batteries. The anion receptor of the present invention is a Lewis acid that can help to dissolve LiF in the passivation films of lithium-ion batteries. Accordingly, one aspect the invention provides electrolytes comprising a lithium salt; a polar aprotic solvent; and an anion receptor additive; and wherein the electrolyte solution is substantially non-aqueous. Further there are provided electrochemical devices employing the electrolyte and methods of making the electrolyte.
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ERIC Educational Resources Information Center
Parry-Jones, R.
1980-01-01
Described are some new uses and procedures of titration procedures. Topics included are titration in non-aqueous solvents, thermometric titration and catalytic methods for end-point detection, titration finish in organic elemental analysis, and sub-micro analysis and automatic titration procedures. (CS)
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Electrochemical Studies of Sulfur Oxychlorides.
1988-03-28
It had been proposed to study sulfuroxyhalides (1) as solutes in a non-aqueous solvent, (2) undiluted, employing lithium tetrachloroaluminate and (3...electrodes in N,N-dimethylforeamide (DNF) with tetra-butylammonium hexafluorophosphate (TBAPF6 ) as supporting electrolyte. Cyclic voltammetry showed
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Zheng, Dong; Yang, Xiao-Qing; Zhang, Xuran
A fast and reliable analytical method is reported for the quantitative determination of dissolved elemental sulfur in non-aqueous electrolytes for Li-S batteries. By using high performance liquid chromatography with a UV detector, the solubility of S in 12 different pure solvents and in 22 different electrolytes was determined. It was found that the solubility of elemental sulfur is dependent on the Lewis basicity, the polarity of solvents and the salt concentration in the electrolytes. In addition, the S content in the electrolyte recovered from a discharged Li-S battery was successfully determined by the proposed HPLC/UV method. Thus, the feasibility ofmore » the method to the online analysis for a Li-S battery is demonstrated. Interestingly, the S was found super-saturated in the electrolyte recovered from a discharged Li-S cell.« less
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Zheng, Dong; Yang, Xiao-Qing; Zhang, Xuran; ...
2014-12-02
A fast and reliable analytical method is reported for the quantitative determination of dissolved elemental sulfur in non-aqueous electrolytes for Li-S batteries. By using high performance liquid chromatography with a UV detector, the solubility of S in 12 different pure solvents and in 22 different electrolytes was determined. It was found that the solubility of elemental sulfur is dependent on the Lewis basicity, the polarity of solvents and the salt concentration in the electrolytes. In addition, the S content in the electrolyte recovered from a discharged Li-S battery was successfully determined by the proposed HPLC/UV method. Thus, the feasibility ofmore » the method to the online analysis for a Li-S battery is demonstrated. Interestingly, the S was found super-saturated in the electrolyte recovered from a discharged Li-S cell.« less
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Brogan, Alex P S; Bui-Le, Liem; Hallett, Jason P
2018-06-25
The increasing requirement to produce platform chemicals and fuels from renewable sources means advances in biocatalysis are rapidly becoming a necessity. Biomass is widely used in nature as a source of energy and as chemical building blocks. However, recalcitrance towards traditional chemical processes and solvents provides a significant barrier to widespread utility. Here, by optimizing enzyme solubility in ionic liquids, we have discovered solvent-induced substrate promiscuity of glucosidase, demonstrating an unprecedented example of homogeneous enzyme bioprocessing of cellulose. Specifically, chemical modification of glucosidase for solubilization in ionic liquids can increase thermal stability to up to 137 °C, allowing for enzymatic activity 30 times greater than is possible in aqueous media. These results establish that through a synergistic combination of chemical biology (enzyme modification) and reaction engineering (solvent choice), the biocatalytic capability of enzymes can be intensified: a key step towards the full-scale deployment of industrial biocatalysis.
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NASA Astrophysics Data System (ADS)
Lerch, Jean-Philippe; Atanase, Leonard Ionut; Riess, Gérard
2017-10-01
A series of non-ionic ABC triblock copolymers, such as poly(butadiene)-b-poly(2-vinylpyrridine)-b-poly(ethylene oxide) (PB-P2VP-PEO) were synthesized by sequential anionic polymerizations. For these copolymers comprising an organo-soluble PB and a water-soluble PEO block, their P2VP middle block has been selected for its anchoring capacity on solid surfaces. The adsorption isotherms on TiO2 were obtained in heptane and in aqueous medium, as selective solvents. In both of these cases, the P2VP middle block provides the surface anchoring, whereas PB and PEO sequences are acting as stabilizing moieties in heptane and water respectively. By extension to ABC triblock copolymers of the scaling theory developed for diblock copolymers, the density of adsorbed chains could be correlated with the molecular characteristics of the PB-P2VP-PEO triblock copolymers. From a practical point a view, it could be demonstrated that these copolymers are efficient dispersing agents for the TiO2 pigments in both aqueous and non-aqueous medium.
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Solvent and process for recovery of hydroxide from aqueous mixtures
Moyer, Bruce A.; Chambliss, C. Kevin; Bonnesen, Peter V.; Keever, Tamara J.
2001-01-01
Hydroxide values and associated alkali metal may be recovered from alkaline aqueous solutions using classes of fluorinated alcohols in a water immiscible solvent. The alcohols are characterized by fluorine substituents which are proximal to the acidic alcohol protons and are located to adjust the acidity of the extractant and the solubility of the extractant in the solvent. A method for stripping the extractant and solvent to regenerate the extractant and purified aqueous hydroxide solution is described.
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Ceramic porous material and method of making same
Liu, Jun; Kim, Anthony Y.; Virden, Jud W.
1997-01-01
The invention is a mesoporous ceramic membrane having substantially uniform pore size. Additionally, the invention includes aqueous and non-aqueous processing routes to making the mesoporous ceramic membranes. According to one aspect of the present invention, inserting a substrate into a reaction chamber at pressure results in reaction products collecting on the substrate and forming a membrane thereon. According to another aspect of the present invention, a second aqueous solution that is sufficiently immiscible in the aqueous solution provides an interface between the two solutions whereon the mesoporous membrane is formed. According to a further aspect of the present invention, a porous substrate is placed at the interface between the two solutions permitting formation of a membrane on the surface or within the pores of the porous substrate. According to yet another aspect of the present invention, mesoporous ceramic materials are formed using a non-aqueous solvent and water-sensitive precursors.
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Ceramic porous material and method of making same
Liu, J.; Kim, A.Y.; Virden, J.W.
1997-07-08
The invention is a mesoporous ceramic membrane having substantially uniform pore size. Additionally, the invention includes aqueous and non-aqueous processing routes to making the mesoporous ceramic membranes. According to one aspect of the present invention, inserting a substrate into a reaction chamber at pressure results in reaction products collecting on the substrate and forming a membrane thereon. According to another aspect of the present invention, a second aqueous solution that is sufficiently immiscible in the aqueous solution provides an interface between the two solutions whereon the mesoporous membrane is formed. According to a further aspect of the present invention, a porous substrate is placed at the interface between the two solutions permitting formation of a membrane on the surface or within the pores of the porous substrate. According to yet another aspect of the present invention, mesoporous ceramic materials are formed using a non-aqueous solvent and water-sensitive precursors. 21 figs.
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Somerset, V; Baker, P; Iwuoha, E
2009-02-01
This paper reports the construction of the gold/mercaptobenzothiazole/polyaniline/acetylcholinesterase/polyvinylacetate (Au/ MBT/PANI/AChE/PVAc) thick-film biosensor for the determination of certain organophosphate pesticide solutions in selected aqueous organic solvent solutions. The Au/MBT/PANI/AChE/PVAc electrocatalytic biosensor device was constructed by encapsulating acetylcholinesterase (AChE) enzyme in the PANI polymer composite, followed by the coating of poly(vinyl acetate) (PVAc) on top to secure the biosensor film from disintegration in the organic solvents evaluated. The electroactive substrate called acetylthiocholine (ATCh) was employed to provide the movement of electrons in the amperometric biosensor. The voltammetric results have shown that the current shifts more anodically as the Au/MBT/PANI/AChE/PVAc biosensor responded to successive acetylthiocholine (ATCh) substrate addition under anaerobic conditions in 0.1 M phosphate buffer, KCl (pH 7.2) solution and aqueous organic solvent solutions. For the Au/MBT/PANI/AChE/PVAc biosensor, various performance and stability parameters were evaluated. These factors include the optimal enzyme loading, effect of pH, long-term stability of the biosensor, temperature stability of the biosensor, the effect of polar organic solvents, and the effect of non-polar organic solvents on the amperometric behavior of the biosensor. The biosensor was then applied to detect a series of 5 organophosphorous pesticides in aqueous organic solvents and the pesticides studied were parathion-methyl, malathion and chlorpyrifos. The results obtained have shown that the detection limit values for the individual pesticides were 1.332 nM (parathion-methyl), 0.189 nM (malathion), 0.018 nM (chlorpyrifos).
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NASA Astrophysics Data System (ADS)
Tomar, Dheeraj S.; Ramesh, Niral; Asthagiri, D.
2018-06-01
We study the solvation free energy of two different conformations (helix and extended) of two different peptides (deca-alanine and deca-glycine) in two different solvents (water and aqueous guanidinium chloride, GdmCl). The free energies are obtained using the quasichemical organization of the potential distribution theorem, an approach that naturally provides the repulsive (solvophobic or cavity) and attractive (solvophilic) contributions to solvation. The solvophilic contribution is further parsed into a chemistry contribution arising from solute interaction with the solvent in the first solvation shell and a long-range contribution arising from non-specific interactions between the solute and the solvent beyond the first solvation shell. The cavity contribution is obtained for two different envelopes, ΣS E, which theory helps identify as the solvent excluded volume, and ΣG, a larger envelope beyond which solute-solvent interactions are Gaussian. The ΣS E envelope is independent of the solvent, as expected on the basis of the insensitivity to the solvent type of the distance of closest approach between protein heavy atoms and solvent heavy atoms, but contrary to the intuition based on treating solvent constituents as spheres of some effective radii. For both envelopes, the cavity contribution in water is proportional to the surface area of the envelope. The same does not hold for GdmCl(aq), revealing the limitation of using molecular area to assess solvation energetics. The ΣG-cavity contribution predicts that GdmCl(aq) should favor the more compact state, contrary to the role of GdmCl in unfolding proteins. The chemistry contribution attenuates this effect, but still the net local (chemistry plus ΣG-packing) contribution is inadequate in capturing the role of GdmCl. With the inclusion of the long-range contribution, which is dominated by van der Waals interaction, aqueous GdmCl favors the extended conformation over the compact conformation. Our finding emphasizes the importance of weak, but attractive, long-range dispersion interactions in protein solution thermodynamics.
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Tomar, Dheeraj S; Ramesh, Niral; Asthagiri, D
2018-06-14
We study the solvation free energy of two different conformations (helix and extended) of two different peptides (deca-alanine and deca-glycine) in two different solvents (water and aqueous guanidinium chloride, GdmCl). The free energies are obtained using the quasichemical organization of the potential distribution theorem, an approach that naturally provides the repulsive (solvophobic or cavity) and attractive (solvophilic) contributions to solvation. The solvophilic contribution is further parsed into a chemistry contribution arising from solute interaction with the solvent in the first solvation shell and a long-range contribution arising from non-specific interactions between the solute and the solvent beyond the first solvation shell. The cavity contribution is obtained for two different envelopes, Σ SE , which theory helps identify as the solvent excluded volume, and Σ G , a larger envelope beyond which solute-solvent interactions are Gaussian. The Σ SE envelope is independent of the solvent, as expected on the basis of the insensitivity to the solvent type of the distance of closest approach between protein heavy atoms and solvent heavy atoms, but contrary to the intuition based on treating solvent constituents as spheres of some effective radii. For both envelopes, the cavity contribution in water is proportional to the surface area of the envelope. The same does not hold for GdmCl(aq), revealing the limitation of using molecular area to assess solvation energetics. The Σ G -cavity contribution predicts that GdmCl(aq) should favor the more compact state, contrary to the role of GdmCl in unfolding proteins. The chemistry contribution attenuates this effect, but still the net local (chemistry plus Σ G -packing) contribution is inadequate in capturing the role of GdmCl. With the inclusion of the long-range contribution, which is dominated by van der Waals interaction, aqueous GdmCl favors the extended conformation over the compact conformation. Our finding emphasizes the importance of weak, but attractive, long-range dispersion interactions in protein solution thermodynamics.
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Spectral Induced Polarization Response of Unconsolidated Saturated Sand and Surfactant Solutions
Dense non-aqueous phase liquids (DNAPL), such as chlorinated solvents, are common groundwater contaminants. Traditional pump-and-treat methods are often not effective at removing residual DNAPL from the subsurface. Surfactant-enhanced aquifer remediation is a promising remediatio...
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Understanding the dissolution of α-zein in aqueous ethanol and acetic acid solutions.
Li, Yunqi; Li, Ji; Xia, Qiuyang; Zhang, Boce; Wang, Qin; Huang, Qingrong
2012-10-04
Zein is a corn prolamin that has broad industrial applications because of its unique physical properties. Currently, the high cost of extraction and purification, which is directly related to the dispersion of zein in different solvents, is the major bottleneck of the zein industry. Solution behaviors of zein have been studied for a long time. However, the physical nature of zein in different solvents remains unclear. In this study, small-angle X-ray scattering (SAXS), static light scattering (SLS), and rheology were combined to study the structure and protein-solvent interaction of α-zein in both acetic acid and aqueous ethanol solutions. We found that the like-dissolve-like rule, the partial unfolding, and the protonation of zein are all critical to understanding the solution behaviors. Zein holds an elongated conformation (i.e., prolate ellipsoid) in all solutions, as revealed from SAXS data. There is an "aging effect" for zein in aqueous ethanol solutions, as evidenced by the transition of Newtonian rheological profiles for fresh zein solutions to the non-Newtonian shear thinning behavior for zein solutions after storage at room temperature for 24 h. Such shear thinning behavior becomes more pronounced for zein solutions at higher concentrations. The SLS results clearly show that acetic acid is a better solvent to dissolve zein than aqueous ethanol solution, as supported by a more negative second virial coefficient. This is majorly caused by the protonation of the protein, which was further verified by the dissolution of zein in water (a nonsolvent for zein) with the addition of acids.
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Quintanar-Guerrero, D; Allémann, E; Fessi, H; Doelker, E
1999-10-25
Pseudolatexes were obtained by a new process based on an emulsification-diffusion technique involving partially water-miscible solvents. The preparation method consisted of emulsifying an organic solution of polymer (saturated with water) in an aqueous solution of a stabilizing agent (saturated with solvent) using conventional stirrers, followed by direct solvent distillation. The technique relies on the rapid displacement of the solvent from the internal into the external phase which thereby provokes polymer aggregation. Nanoparticle formation is believed to occur because rapid solvent diffusion produces regions of local supersaturation near the interface, and nanoparticles are formed due to the ensuing interfacial phase transformations and polymer aggregation that occur in these interfacial domains. Using this method, it was possible to prepare pseudolatexes of biodegradable and non-biodegradable polymers such as poly(D,L-lactic acid) and poly(epsilon-caprolactone), Eudragit E, cellulose acetate phthalate, cellulose acetate trimellitate using ethyl acetate or 2-butanone as partially water-miscible solvents and poly(vinyl alcohol) or poloxamer 407 as stabilizing agent. A transition from nano- to microparticles was observed at high polymer concentrations. At concentrations above 30% w/v of Eudragit E in ethyl acetate or cellulose acetate phthalate in 2-butanone only microparticles were obtained. This behaviour was attributed to decreased transport of polymer molecules into the aqueous phase.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Jansen, Andrew N.; Vaughey, John T.; Chen, Zonghai
The present invention provides a non-aqueous redox flow battery comprising a negative electrode immersed in a non-aqueous liquid negative electrolyte, a positive electrode immersed in a non-aqueous liquid positive electrolyte, and a cation-permeable separator (e.g., a porous membrane, film, sheet, or panel) between the negative electrolyte from the positive electrolyte. During charging and discharging, the electrolytes are circulated over their respective electrodes. The electrolytes each comprise an electrolyte salt (e.g., a lithium or sodium salt), a transition-metal free redox reactant, and optionally an electrochemically stable organic solvent. Each redox reactant is selected from an organic compound comprising a conjugated unsaturatedmore » moiety, a boron cluster compound, and a combination thereof. The organic redox reactant of the positive electrolyte is selected to have a higher redox potential than the redox reactant of the negative electrolyte.« less
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Rohan, Amy L; Switzer, Jackson R; Flack, Kyle M; Hart, Ryan J; Sivaswamy, Swetha; Biddinger, Elizabeth J; Talreja, Manish; Verma, Manjusha; Faltermeier, Sean; Nielsen, Paul T; Pollet, Pamela; Schuette, George F; Eckert, Charles A; Liotta, Charles L
2012-11-01
Silylamine reversible ionic liquids were designed to achieve specific physical properties in order to address effective CO₂ capture. The reversible ionic liquid systems reported herein represent a class of switchable solvents where a relatively non-polar silylamine (molecular liquid) is reversibly transformed to a reversible ionic liquid (RevIL) by reaction with CO₂ (chemisorption). The RevILs can further capture additional CO₂ through physical absorption (physisorption). The effects of changes in structure on (1) the CO₂ capture capacity (chemisorption and physisorption), (2) the viscosity of the solvent systems at partial and total conversion to the ionic liquid state, (3) the energy required for reversing the CO₂ capture process, and (4) the ability to recycle the solvents systems are reported. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Pilot-Scale Silicone Process for Low-Cost Carbon Dioxide Capture. Final Scientific/Technical Report
DOE Office of Scientific and Technical Information (OSTI.GOV)
Hancu, Dan; Wood, Benjamin; Genovese, Sarah
GE Global Research has developed, over the last 8 years, a platform of cost effective CO 2 capture technologies based on a non-aqueous aminosilicone solvent (GAP-1m). As demonstrated in a previous funded DOE project (DE-FE0007502), the GAP-1m solvent has increased CO 2 working capacity, lower volatility and corrosivity than the benchmark aqueous amine technology. The current report describes the cooperative program between GE Global Research (GE GRC), and the National Carbon Capture Center (NCCC) to design, construct, and operate a pilot-scale process using GAP-1m solvent to demonstrate its performance at 0.5 MWe. (i) Performance of the GAP-1m solvent was demonstratedmore » in a 0.5 MWe pilot with real flue gas for over 900 hrs. of operation using two alternative desorption designs: a Continuous Stirred Tank Reactor (CSTR), and a Steam Stripper Column (SSC). The CSTR is a one-stage separation unit with reduced space requirements, and capital cost. The alternative is a multi-stage separation column, with improved desorption efficiency. Testing the two desorber options allowed us to identify the most cost effective, and space efficient desorber solution. (ii) CSTR Campaign: The CSTR desorber unit was designed, fabricated and integrated with the pilot solvent test unit (PSTU), replacing the PSTU Steam Stripper Column at NCCC. Solvent management and waste water special procedures were implemented to accommodate operation of the non-aqueous solvent in the PSTU. Performance of the GAP-1m solvent with the CSTR was demonstrated for over 500 hrs. while varying temperature of the desorption (230 – 265 oF), solvent circulation rate (GAP-1m : CO 2 (molar) = 1.5 – 4), and flue gas flow rates (0.2 – 0.5 MWe). Solvent carry-over in the CO 2 product was minimized by maintaining water content below 5 wt.%, and desorption pressure at 7 psig. CO 2 capture efficiency achieved was 95% at 0.25 MWe (GAP-1m : CO 2 = 4 (molar), 230 oF desorption), and 65% at 0.5 MWe (GAP-1m : CO 2 (molar) = 1.5, 248 oF). Solvent loss was dominated by thermal degradation of the rich solvent. (iii) Steam Stripper Column Campaign: Higher expected cost of the solvent vs. aqueous amines makes solvent management a top priority to maintain the low cost for the process. During the testing of the GAP-1m solvent with the CSTR, thermal degradation of the rich solvent was found to be the main mechanism in solvent loss. Small amounts of water in the working solution were found to be an effective way to enable steam stripping, thereby lowering desorption temperature, and hence reducing thermal degradation. Steam stripping also increased working capacity by 30% due to a more efficient desorption. The concept was first tested in a glass stripping column (lab scale, GE GRC), optimized in a continuous bench scale system (2 kWe, GE GRC), and demonstrated in a 0.5 MWe PSTU at NCCC. No special system modifications were required to the PSTU to accommodate the testing of the non-aqueous GAP-1 solvent with the regenerator column. SSC was found to be more robust towards solvent entrainment (H 2O < 35 wt.%). 90 – 95% CO 2 capture efficiency was achieved under stoichiometric conditions at 0.5 MWe (235 oF desorption, 2 psig and 19 wt. % H 2O). Both CO 2 capture efficiency and specific duty reached optimum conditions at 18 wt.% H 2O. Low amine degradation (< 0.05 wt.%/day) was recorded over 350 hrs. of operation. Controlled water addition to GAP-1m solvent decreased the desorption temperature, thermal degradation, and improved the CO 2 working capacity due to more efficient absorption and desorption processes. Under these conditions, the GAP-1m solvent exhibited a 25% increased working capacity, and 10% reduction in specific steam duty vs. MEA, at 10 oF lower desorption temperature. (iv) Techno-economic Analysis: The pilot-scale PSTU engineering data were used to update the capture system process models, and the techno-economic analysis was performed for a 550 MW coal fired power plant. The 1st year CO 2 removal cost for the aminosilicone-based carbon-capture process was evaluated at $48/ton CO 2 using the steam stripper column. This is a 20% reduction compared to MEA, primarily due to lower overall capital cost. CO 2 cost using the CSTR desorber is dominated by the economics of the solvent make-up. The steam stripper desorber is the preferred unit operation due to a more efficient desorption, and reduced solvent make-up rate. Further reduction in CO 2 capture cost is expected by lowering the manufacturing cost of the solvent, implementing flowsheet optimization and/or implementing the next generation aminosilicone solvent with improved stability and increased CO 2 working capacity.« less
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Rainey, R.H.; Moore, J.G.
1962-08-14
A liquid-liquid extraction process was developed for recovering thorium and uranium values from a neutron irradiated thorium composition. They are separated from a solvent extraction system comprising a first end extraction stage for introducing an aqueous feed containing thorium and uranium into the system consisting of a plurality of intermediate extractiorr stages and a second end extractron stage for introducing an aqueous immiscible selective organic solvent for thorium and uranium in countercurrent contact therein with the aqueous feed. A nitrate iondeficient aqueous feed solution containing thorium and uranium was introduced into the first end extraction stage in countercurrent contact with the organic solvent entering the system from the second end extraction stage while intro ducing an aqueous solution of salting nitric acid into any one of the intermediate extraction stages of the system. The resultant thorium and uranium-laden organic solvent was removed at a point preceding the first end extraction stage of the system. (AEC)
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Liu, Hui; Chen, Fu; Sun, Huiyong; Li, Dan; Hou, Tingjun
2017-04-11
By means of estimators based on non-equilibrium work, equilibrium free energy differences or potentials of mean force (PMFs) of a system of interest can be computed from biased molecular dynamics (MD) simulations. The approach, however, is often plagued by slow conformational sampling and poor convergence, especially when the solvent effects are taken into account. Here, as a possible way to alleviate the problem, several widely used implicit-solvent models, which are derived from the analytic generalized Born (GB) equation and implemented in the AMBER suite of programs, were employed in free energy calculations based on non-equilibrium work and evaluated for their abilities to emulate explicit water. As a test case, pulling MD simulations were carried out on an alanine polypeptide with different solvent models and protocols, followed by comparisons of the reconstructed PMF profiles along the unfolding coordinate. The results show that when employing the non-equilibrium work method, sampling with an implicit-solvent model is several times faster and, more importantly, converges more rapidly than that with explicit water due to reduction of dissipation. Among the assessed GB models, the Neck variants outperform the OBC and HCT variants in terms of accuracy, whereas their computational costs are comparable. In addition, for the best-performing models, the impact of the solvent-accessible surface area (SASA) dependent nonpolar solvation term was also examined. The present study highlights the advantages of implicit-solvent models for non-equilibrium sampling.
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D'Autry, Ward; Zheng, Chao; Wolfs, Kris; Yarramraju, Sitaramaraju; Hoogmartens, Jos; Van Schepdael, Ann; Adams, Erwin
2011-06-01
Static headspace (HS) sampling has been commonly used to test for volatile organic chemicals, usually referred to as residual solvents (RS) in pharmaceuticals. If the sample is not soluble in water, organic solvents are used. However, these seriously reduce the sensitivity in the determination of some RS. Here, mixed aqueous dilution media (a mixture of water and an organic solvent like dimethyl formamide, dimethyl sulfoxide or dimethyl acetamide) were studied as alternative media for static HS-gas chromatographic analysis. Although it has been known that mixed aqueous dilution media can often improve sensitivity for many RS, this study used a systematic approach to investigate phase volumes and the organic content in the HS sampling media. Reference solutions using 18 different class 1, 2 and 3 RS were evaluated. The effect of salt addition was also studied in this work. A significant increase in the peak area was observed for all RS using mixed aqueous dilution media, when compared with organic solvents alone. Matrix effects related to the mixed aqueous dilution media were also investigated and reported. Repeatability and linearity obtained with mixed aqueous dilution media were found to be similar to those observed with pure organic solvents. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Microcapsules and Methods for Making
NASA Technical Reports Server (NTRS)
Morrison, Dennis R. (Inventor); Mosier, Benjamin (Inventor)
1998-01-01
Methods of forming multi-lamellar microcapsules having alternating layers of hydrophilic and hydrophobic immiscible liquid phases have been developed using different polymer/solvent systems. The methods use liquid-liquid diffusion and simultaneous lateral phase separation, controlled by proper timed-sequence exposures of immiscible phases and low shear mixing, to form narrow size distributions of spherical, multilamellar microcapsules. The use of special formulations of solubilized drugs, surfactants, and polymeric co-surfactants in aqueous vehicles which are dispersed in hydrocarbon solvents containing small quantities of oil, low molecular weight co-surfactants and glycerides that are aqueous insoluble enables the formation of unique microcapsules which can carry large amounts of pharmaceuticals in both aqueous and non-aqueous solvent compartments. The liquid microcapsules are quickly formed in a single step and can include a polymeric outer 'skin' which protects the microcapsules during physical manipulation or exposure to high shear forces. Water-in-oil and oil-in-water microcapsules have been formed both in 1 x g and in microgravity, which contain several types of drugs co-encapsulated within different fluid compartments inside the same microcapsule. Large, spherical multi-lamellar microcapsules have been formed including a cytotoxic drug co-encapsulated with a radiocontrast medium which has advantages for chemoembolization of vascular tumors. In certain cases, crystals of the drug form inside the microcapsules providing zero-order and first order, sustained drug release kinetics.
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1997-03-01
volatile organic compounds (VOCs), dense non-aqueous phase liquids (DNAPLs), and permeable reactive walls for chlorinated solvents The GRFL is the only... compounds , solvents, and heavy metals. SCAPS technology has been demonstrated to reduce the costs of traditional site screening by up to 90 percent; it...styphnate and volatile organic compounds (VOCs). Hazardous wastes also are generated during demilitarization. Under partial sponsorship of SERDP, the US Army
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NEPTUNIUM SOLVENT EXTRACTION PROCESS
Dawson, L.R.; Fields, P.R.
1959-10-01
The separation of neptunium from an aqueous solution by solvent extraction and the extraction of neptunium from the solvent solution are described. Neptunium is separated from an aqueous solution containing tetravalent or hexavalent neptunium nitrate, nitric acid, and a nitrate salting out agent, such as sodium nitrate, by contacting the solution with an organic solvent such as diethyl ether. Subsequently, the neptunium nitrate is extracted from the organic solvent extract phase with water.
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RECOVERY OF METAL VALUES FROM AQUEOUS SOLUTIONS BY SOLVENT EXTRACTION
Moore, R.L.
1959-09-01
An organic solvent mixure is described for extracting actinides from aqueous solutions; the solvent mixture consists of from 10 to 25% by volume of tributyl phosphate and the remainder a chlorine-fluorine-substituted saturated hydrocarbon having two carbon atoms in the molecule.
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NASA Astrophysics Data System (ADS)
Phifer, Jeremy R.; Cox, Courtney E.; da Silva, Larissa Ferreira; Nogueira, Gabriel Gonçalves; Barbosa, Ana Karolyne Pereira; Ley, Ryan T.; Bozada, Samantha M.; O'Loughlin, Elizabeth J.; Paluch, Andrew S.
2017-06-01
Methods to predict the equilibrium solubility of non-electrolyte solids are important for the design of novel separation processes. Here we demonstrate how conventional molecular simulation free energy calculations or electronic structure calculations in a continuum solvent, here SMD or SM8, can be used to predict parameters for the MOdified Separation of Cohesive Energy Density (MOSCED) method. The method is applied to the solutes naphthalene, anthracene, phenanthrene, pyrene and dibenzothiophene, compounds of interested to the petroleum industry and for environmental remediation. Adopting the melting point temperature and enthalpy of fusion of these compounds from experiment, we are able to predict equilibrium solubilities. Comparing to a total of 422 non-aqueous and 193 aqueous experimental solubilities, we find the proposed method is able to well correlate the data. The use of MOSCED is additionally advantageous as it is a solubility parameter-based method useful for intuitive solvent selection and formulation.
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Mixed solvent electrolytes for ambient temperature secondary lithium cells
NASA Technical Reports Server (NTRS)
Shen, David H. (Inventor); Surampudi, Subbarao (Inventor); Deligiannis, Fotios (Inventor); Halpert, Gerald (Inventor)
1991-01-01
The present invention comprises an improved electrolyte for secondary lithium-based cells as well as batteries fabricated using this electrolyte. The electrolyte is a lithium containing salt dissolved in a non-aqueous solvent, which is made from a mixture of ethylene carbonate, ethylene propylene diene terpolymer, 2-methylfuran, and 2-methyltetrahydrofuran. This improved, mixed solvent electrolyte is more conductive than prior electrolytes and much less corrosive to lithium anodes. Batteries constructed with this improved electrolyte utilize lithium or lithium alloy anodes and cathodes made of metal chalcogenides or oxides, such as TiS.sub.2, NbSe.sub.3, V.sub.6 O.sub.13, V.sub.2 O.sub.5, MoS.sub.2, MoS.sub.3, CoO.sub.2, or CrO.sub.2, dissolved in a supporting polymer matrix, like EPDM. The preferred non-aqueous solvent mixture comprises approximately 5 to 30 volume percent ethylene carbonate, approximately 0.01 to 0.1 weight percent ethylene propylene diene terpolymer, and approximately 0.2 to 2 percent 2-methylfuran, with the balance being 2-methyltetrahydrofuran. The most preferred solvent comprises approximately 10 to 20 volume percent ethylene carbonate, about 0.05 weight percent ethylene propylene diene terpolymer, and about 1.0 percent 2-methylfuran, with the balance being 2-methyltetrahydrofuran. The concentration of lithium arsenic hexafluoride can range from about 1.0 to 1.8 M; a concentration 1.5 M is most preferred. Secondary batteries made with the improved electrolyte of this invention have lower internal impedance, longer cycle life, higher energy density, low self-discharge, and longer shelf life.
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Wan, Ying-chun; Ma, Hui-ting; Lu, Bin
2015-01-01
When organic solvent-compatible molecularly imprinted polymers (MIPs) are used in aqueous environment, how to reduce nonspecific binding is a major challenge. By modifying the binding solvents and introducing appropriate washing and elution steps, even relatively hydrophobic MIPs can gain optimal rebinding selectivity in aqueous conditions. Furthermore, water-compatible MIPs that can be used to treat aqueous samples directly have been prepared. The use of hydrophilic co-monomers, the controlled surface modification through controlled radical polymerization, and the new interfacial molecular imprinting methods are different strategies to prepare water-compatible MIPs. By combining MIPs with other techniques, both organic solvent-compatible and water-compatible MIPs can display better functional performances in aqueous conditions. Intensive studies on MIPs in aqueous conditions can provide new MIPs with much-improved compatibilities that will lead to more interesting applications in biomedicine and biotechnology.
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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.
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Preferential solvation of lithium cations and impacts on oxygen reduction in lithium–air batteries
DOE Office of Scientific and Technical Information (OSTI.GOV)
Zheng, Dong; Qu, Deyu; Yang, Xiao -Qing
2015-09-16
The solvation of Li⁺ with eleven non-aqueous solvents commonly used as the electrolytes for Li batteries were studied. The solvation preferences of different solvents were compared by means of electrospray mass spectrometry and collision-induced dissociation. The relative strength of the solvent for the solvation of Li⁺ was determined. The Lewis acidity of the solvated Li⁺ cations was determined by the preferential solvation of the solvent in the solvation shell. The kinetics of the catalytic disproportionation of the O₂⁻ depends on the relative Lewis acidity of the solvated Li⁺ ion. The impact of the solvated Li⁺ cation on the O₂ redoxmore » reaction was also investigated.« less
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High energy density battery based on complex hydrides
Zidan, Ragaiy
2016-04-26
A battery and process of operating a battery system is provided using high hydrogen capacity complex hydrides in an organic non-aqueous solvent that allows the transport of hydride ions such as AlH.sub.4.sup.- and metal ions during respective discharging and charging steps.
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Aspects of Solvent Chemistry for Calcium Hydroxide Medicaments
Athanassiadis, Basil
2017-01-01
Calcium hydroxide pastes have been used in endodontics since 1947. Most current calcium hydroxide endodontic pastes use water as the vehicle, which limits the dissolution of calcium hydroxide that can be achieved and, thereby, the maximum pH that can be achieved within the root canal system. Using polyethylene glycol as a solvent, rather than water, can achieve an increase in hydroxyl ions release compared to water or saline. By adopting non-aqueous solvents such as the polyethylene glycols (PEG), greater dissolution and faster hydroxyl ion release can be achieved, leading to enhanced antimicrobial actions, and other improvements in performance and biocompatibility. PMID:29065542
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Almandoz, M C; Sancho, M I; Duchowicz, P R; Blanco, S E
2014-08-14
The solvatochromic behavior of trimethoprim (TMP) was analyzed using UV-Vis spectroscopy and DFT methods in neat and binary aqueous solvent mixtures. The effects of solvent dipolarity/polarizability and solvent-solute hydrogen bonding interactions on the absorption maxima were evaluated by means of the linear solvation energy relationship concept of Kamlet and Taft. This analysis indicated that both interactions play an important role in the position of the absorption maxima in neat solvents. The simulated absorption spectra of TMP and TMP:(solvent)n complexes in ACN and H2O using TD-DFT methods were in agreement with the experimental ones. Binary aqueous mixtures containing as co-solvents DMSO, ACN and EtOH were studied. Preferential solvation was detected as a nonideal behavior of the wavenumber curve respective to the analytical mole fraction of co-solvent in all binary systems. TMP molecules were preferentially solvated by the organic solvent over the whole composition range. Index of preferential solvation, as well as the influence of solvent parameters were calculated as a function of solvent composition. Copyright © 2014 Elsevier B.V. All rights reserved.
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2018-01-01
This work focuses on the process development of membrane-assisted solvent extraction of hydrophobic compounds such as monoterpenes. Beginning with the choice of suitable solvents, quantum chemical calculations with the simulation tool COSMO-RS were carried out to predict the partition coefficient (logP) of (S)-(+)-carvone and terpinen-4-ol in various solvent–water systems and validated afterwards with experimental data. COSMO-RS results show good prediction accuracy for non-polar solvents such as n-hexane, ethyl acetate and n-heptane even in the presence of salts and glycerol in an aqueous medium. Based on the high logP value, n-heptane was chosen for the extraction of (S)-(+)-carvone in a lab-scale hollow-fibre membrane contactor. Two operation modes are investigated where experimental and theoretical mass transfer values, based on their related partition coefficients, were compared. In addition, the process is evaluated in terms of extraction efficiency and overall product recovery, and its biotechnological application potential is discussed. Our work demonstrates that the combination of in silico prediction by COSMO-RS with membrane-assisted extraction is a promising approach for the recovery of hydrophobic compounds from aqueous solutions. PMID:29765654
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Salting out the polar polymorph: analysis by alchemical solvent transformation.
Duff, Nathan; Dahal, Yuba Raj; Schmit, Jeremy D; Peters, Baron
2014-01-07
We computationally examine how adding NaCl to an aqueous solution with α- and γ-glycine nuclei alters the structure and interfacial energy of the nuclei. The polar γ-glycine nucleus in pure aqueous solution develops a melted layer of amorphous glycine around the nucleus. When NaCl is added, a double layer is formed that stabilizes the polar glycine polymorph and eliminates the surface melted layer. In contrast, the non-polar α-glycine nucleus is largely unaffected by the addition of NaCl. To quantify the stabilizing effect of NaCl on γ-glycine nuclei, we alchemically transform the aqueous glycine solution into a brine solution of glycine. The alchemical transformation is performed both with and without a nucleus in solution and for nuclei of α-glycine and γ-glycine polymorphs. The calculations show that adding 80 mg/ml NaCl reduces the interfacial free energy of a γ-glycine nucleus by 7.7 mJ/m(2) and increases the interfacial free energy of an α-glycine nucleus by 3.1 mJ/m(2). Both results are consistent with experimental reports on nucleation rates which suggest: J(α, brine) < J(γ, brine) < J(α, water). For γ-glycine nuclei, Debye-Hückel theory qualitatively, but not quantitatively, captures the effect of salt addition. Only the alchemical solvent transformation approach can predict the results for both polar and non-polar polymorphs. The results suggest a general "salting out" strategy for obtaining polar polymorphs and also a general approach to computationally estimate the effects of solvent additives on interfacial free energies for nucleation.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Taylor-Pashow, Kathryn M. L.; Jones, Daniel H.
A non-aqueous titration method has been used for quantifying the suppressor concentration in the MCU solvent hold tank (SHT) monthly samples since the Next Generation Solvent (NGS) was implemented in 2013. The titration method measures the concentration of the NGS suppressor (TiDG) as well as the residual tri-n-octylamine (TOA) that is a carryover from the previous solvent. As the TOA concentration has decreased over time, it has become difficult to resolve the TiDG equivalence point as the TOA equivalence point has moved closer. In recent samples, the TiDG equivalence point could not be resolved, and therefore, the TiDG concentration wasmore » determined by subtracting the TOA concentration as measured by semi-volatile organic analysis (SVOA) from the total base concentration as measured by titration. In order to improve the titration method so that the TiDG concentration can be measured directly, without the need for the SVOA data, a new method has been developed that involves spiking of the sample with additional TOA to further separate the two equivalence points in the titration. This method has been demonstrated on four recent SHT samples and comparison to results obtained using the SVOA TOA subtraction method shows good agreement. Therefore, it is recommended that the titration procedure be revised to include the TOA spike addition, and this to become the primary method for quantifying the TiDG.« less
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Trichloroethylene (TCE) is widely used as a solvent in metal processing and electronic manufacturing industries, but waste and spilled TCE often results in blocks of non-aqueous liquid in vadose and saturated zones which become continuous contamination sources for groundwater. El...
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Method 8321B describes procedures for preparation and analysis of solid, aqueous liquid, drinking water and wipe samples using high performance liquid chromatography and mass spectrometry for extractable non-volatile compounds.
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Solvation models, based on fundamental chemical structure theory, were developed in the SPARC mechanistic tool box to predict a large array of physical properties of organic compounds in water and in non-aqueous solvents strictly from molecular structure. The SPARC self-interact...
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Tetrachloroethylene (PCE), typically used as a dry cleaning solvent, is a predominant contaminant in the subsurface at Superfund Sites. PCE is a dense non-aqueous phase liquid (DNAPL) that migrates downward into the earth, leaving behind areas of residual saturation and free prod...
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A wide variety of in situ subsurface remediation strategies have been developed to mitigate contamination by chlorinated solvent dense non-aqueous phase liquids (DNAPLS) and metals. Geochemical methods include: zerovalent iron emplacement, various electrolytic applications, elec...
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Pavlov, Julius; Braida, Washington; Ogundipe, Adebayo; O'Connor, Gregory; Attygalle, Athula B
2009-10-01
The presence of a peak centered near m/z 2862, observed for the first time for the caged dodecatungstate radical-anion, [W12O41]-*, enables distinguishing WO2 from WO3 by Laser Desorption Ionization mass spectrometry (LDI-MS). In addition to WO2, laser irradiation of dry deposits made from aqueous ammonium paratungstate, and calcium and lead orthotungstate also produce the [W12O41]-. In contrast, spectra recorded from deposits made from aqueous Na2WO4, sodium metatungstate, and WO3, or non-aqueous calcium and lead orthotungstate, and ammonium paratungstate, failed to show the m/z 2862 peak cluster. These observations support the hypothesis that polycondensation reactions to form [W12O41]-* occur solely in the presence of water. Although dry spots are irradiated for ionization, the solvent used for sample preparation plays an important role on the chemical composition endowed to ions detected. For example, the m/z 2862 peak seen from deposits made from aqueous ammonium paratungstate, and calcium and lead orthotungstate, is absent in the spectra recorded either from pristine deposits or those derived from solutions made with organic solvents such as acetonitrile or ethanol.
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Towards water compatible MIPs for sensing in aqueous media.
Horemans, F; Weustenraed, A; Spivak, D; Cleij, T J
2012-06-01
When synthesizing molecularly imprinted polymers (MIPs), a few fundamental principles should be kept in mind. There is a strong correlation between porogen polarity, MIP microenvironment polarity and the imprinting effect itself. The combination of these parameters eventually determines the overall binding behavior of a MIP in a given solvent. In addition, it is shown that MIP binding is strongly influenced by the polarity of the rebinding solvent. Because the use of MIPs in biomedical environments is of considerable interest, it is important that these MIPs perform well in aqueous media. In this article, various approaches are explored towards a water compatible MIP for the target molecule l-nicotine. To this end, the imprinting effect together with the MIP matrix polarity is fine-tuned during MIP synthesis. The binding behavior of the resulting MIPs is evaluated by performing batch rebinding experiments that makes it possible to select the most suitable MIP/non-imprinted polymer couple for future application in aqueous environments. One method to achieve improved compatibility with water is referred to as porogen tuning, in which porogens of varying polarities are used. It is demonstrated that, especially when multiple porogens are mixed, this approach can lead to superior performance in aqueous environments. Another method involves the incorporation of polar or non-polar comonomers in the MIP matrix. It is shown that by carefully selecting these monomers, it is also possible to obtain MIPs, which can selectively bind their target in water. Copyright © 2012 John Wiley & Sons, Ltd.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Maddi, Balakrishna; Panisko, Ellen; Albrecht, Karl
Two-dimensional gas chromatography coupled with time of flight mass spectrometry is a powerful tool for identifying and quantifying components in complex mixtures. It has been used to analyze gasoline, jet fuel, diesel, bio-diesel and organic fraction of bio-crude/bio-oil. In these experiments, the first dimension of separation was non-polar, followed by a polar separation. Aqueous fractions of bio-crude and other aqueous samples have been examined with similar column combinations. However, sample preparation techniques such as derivatization, solvent extraction, and solid-phase extraction were necessary prior to analysis. In this study, aqueous fraction obtained from hydrothermal liquefaction of algae was characterized by two-dimensionalmore » gas chromatography coupled with time of flight mass spectrometry without prior sample preparation techniques using a polar separation in the first dimension followed by a non-polar separation. Two-dimensional plots from this analysis were compared with those obtained from the more traditional column combination. Results from qualitative characterization aqueous fractions of algal bio-crude are discussed in detail. The advantages of using a polar separation followed by a non-polar separation for characterization of organics in aqueous samples by two-dimensional gas chromatography coupled with time of flight mass spectrometry are highlighted.« less
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Investigation of Ion-Solvent Interactions in Nonaqueous Electrolytes Using in Situ Liquid SIMS
DOE Office of Scientific and Technical Information (OSTI.GOV)
Zhang, Yanyan; Su, Mao; Yu, Xiaofei
2018-02-06
Ion-solvent interactions in non-aqueous electrolytes are of fundamental interest and practical importance, yet debates regarding ion preferential solvation and coordination numbers persist. In this work, in situ liquid SIMS was used to examine ion-solvent interactions in three representative electrolytes, i.e., lithium hexafluorophosphate (LiPF6) at 1.0 M in ethylene carbonate (EC)-dimethyl carbonate (DMC), and lithium bis(fluorosulfonyl)imide (LiFSI) at both low (1.0 M) and high (4.0 M) concentrations in 1,2-dimethoxyethane (DME). In the positive ion mode, solid molecular evidence strongly supports the preferential solvation of Li+ by EC. Besides, from the negative spectra, we also found that PF6- forms association with EC,more » which has been neglected by previous studies due to the relatively weak interaction. While in both LiFSI in DME electrolytes, no evidence shows that FSI- is associated with DME. Furthermore, strong salt ion cluster signals were observed in the 1.0 M LiPF6 in EC-DMC electrolyte, suggesting that a significant amount of Li+ ions stay in vicinity of anions. In sharp comparison, weak ion cluster signals were detected in dilute LiFSI in DME electrolyte, suggesting most ions are well separated, in agreement with our molecular dynamics (MD) simulation results. These findings indicate that with virtues of little bias on detecting positive and negative ions and the capability of directly analyzing concentrated electrolytes, in situ liquid SIMS is a powerful tool that can provide key evidence for improved understanding on the ion-solvent interactions in non-aqueous electrolytes. Therefore, we anticipate wide applications of in situ liquid SIMS on investigations of various ion-solvent interactions in the near future.« less
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Investigation of Ion–Solvent Interactions in Nonaqueous Electrolytes Using in Situ Liquid SIMS
DOE Office of Scientific and Technical Information (OSTI.GOV)
Zhang, Yanyan; Su, Mao; Yu, Xiaofei
Ion-solvent interactions in non-aqueous electrolytes are of fundamental interest and practical importance, yet debates regarding ion preferential solvation and coordination numbers persist. In this work, in situ liquid SIMS was used to examine ion-solvent interactions in three representative electrolytes, i.e., lithium hexafluorophosphate (LiPF6) at 1.0 M in ethylene carbonate (EC)-dimethyl carbonate (DMC), and lithium bis(fluorosulfonyl)imide (LiFSI) at both low (1.0 M) and high (4.0 M) concentrations in 1,2-dimethoxyethane (DME). In the positive ion mode, solid molecular evidence strongly supports the preferential solvation of Li+ by EC. Besides, from the negative spectra, we also found that PF6- forms association with EC,more » which has been neglected by previous studies due to the relatively weak interaction. While in both LiFSI in DME electrolytes, no evidence shows that FSI- is associated with DME. Furthermore, strong salt ion cluster signals were observed in the 1.0 M LiPF6 in EC-DMC electrolyte, suggesting that a significant amount of Li+ ions stay in vicinity of anions. In sharp comparison, weak ion cluster signals were detected in dilute LiFSI in DME electrolyte, suggesting most ions are well separated, in agreement with our molecular dynamics (MD) simulation results. These findings indicate that with virtues of little bias on detecting positive and negative ions and the capability of directly analyzing concentrated electrolytes, in situ liquid SIMS is a powerful tool that can provide key evidence for improved understanding on the ion-solvent interactions in non-aqueous electrolytes. Therefore, we anticipate wide applications of in situ liquid SIMS on investigations of various ion-solvent interactions in the near future.« less
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RECOVERY OF PROTACTINIUM FROM AQUEOUS SOLUTIONS
Elson, R.E.
1959-07-14
The recovery of fluoride complexed protactinium from aqueous acidic solutions by solvent extraction is described. Generally the prccess of the invention com rises mixing an aqueous solution containing protactinium in a complexed form with an organic solvent which is specific for protactinium, such as diisopropyl carbinol, then decomposing the protactinium complex by adjusting the acidity of the aqueous solution to between 0-3 to 0-9 M in hydrogen ion concentration, and introducing a source of aluminum ions in sufficient quantity to establish a concentration of 0.5 to 1.2 M aluminum ion, whereupon decomposition of the protactinium fluoride complex takes place and the protactinium ion is taken up by the organic solvent phase.
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de Faria, Emanuelle L P; do Carmo, Rafael S; Cláudio, Ana Filipa M; Freire, Carmen S R; Freire, Mara G; Silvestre, Armando J D
2017-10-30
In recent years a high demand for natural ingredients with nutraceutical properties has been witnessed, for which the development of more environmentally-friendly and cost-efficient extraction solvents and methods play a primary role. In this perspective, in this work, the application of deep eutectic solvents (DES), composed of quaternary ammonium salts and organic acids, as alternative solvents for the extraction of cynaropicrin from Cynara cardunculus L. leaves was studied. After selecting the most promising DES, their aqueous solutions were investigated, allowing to obtain a maximum cynaropicrin extraction yield of 6.20 wt %, using 70 wt % of water. The sustainability of the extraction process was further optimized by carrying out several extraction cycles, reusing either the biomass or the aqueous solutions of DES. A maximum cynaropicrin extraction yield of 7.76 wt % by reusing the solvent, and of 8.96 wt % by reusing the biomass, have been obtained. Taking advantage of the cynaropicrin solubility limit in aqueous solutions, water was added as an anti-solvent, allowing to recover 73.6 wt % of the extracted cynaropicrin. This work demonstrates the potential of aqueous solutions of DES for the extraction of value-added compounds from biomass and the possible recovery of both the target compounds and solvents.
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Determination of organic bases in non-aqueous solvents by catalytic thermometric titration.
Vajgand, V J; Kiss, T A; Gaál, F F; Zsigrai, I J
1968-07-01
Catalytic thermometric titrations have been developed for bases (brucine, diethylaniline, potassium acetate and triethylamine) in acetic acid by continuous and discontinuous addition of the standard solution and automatic temperature recording. The determination of weak bases, e.g., antipyrine, unsuccessful in acetic acid by catalytic thermometric titration, has been achieved by using nitromethane or acetic anhydride as solvent. Catalytic thermometric titrations were also performed by coulometric generation of hydrogen ions for the determination of micro amounts of weak bases in a mixture of acetic anhyride and acetic acid.
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NASA Astrophysics Data System (ADS)
Indarti, E.; Marwan; Wanrosli, W. D.
2015-06-01
Nanocrystallinecellulose (NCC) from biomass is a promising material with huge potentials in various applications. A big challenge in its utilization is the agglomeration of the NCC's during processing due to hydrogen bonding among the cellulose chains when in close proximity to each other. Obtaining NCC's in a non-agglomerated and non-aqueous condition is challenging. In the present work NCC's was isolated from oil palm empty fruit bunch (OPEFB) using TEMPO-oxidation reaction method. To obtain non-agglomerated and non-aqueous products, the NCC's underwent post-treatment using oven drying (OD) and solvent exchanged (SE) techniques. The thermal stability of all samples was determined from TGA and DTG profiles whilst FTIR was used to analyzethe chemical modifications that occurred under these conditions. NCC-SE has better thermal stability than the NCC-OD and its on-set degradation temperature and residue are also higher. FTIR analysis shows that NCC-SE has a slightly different chemical composition whereby the absorption band at 1300 cm-1 (due to C-O symmetric stretching) is absent as compared to NCC-OD indicating that in NCC-SE the carboxylate group is in acid form which contribute to its thermal stability
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Cheng, Lizhen; Gai, Xiumei; Wen, Haoyang; Liu, Dandan; Tang, Xin; Wang, Yanyan; Wang, Tuanjie; Pan, Weisan; Yang, Xinggang
2018-01-01
The objective of this study was to investigate the fundamental properties of propranolol hydrochloride osmotic pump tablets coated by aqueous polymer dispersion, simultaneously exploring the in vitro and in vivo correlation of the tablet. The physicochemical properties and parameters of aqueous polymer dispersion membranes (SEM, water uptake, and water vapor transmission coefficient) were investigated. In addition, the release behavior and the in vitro release and in vivo absorption profiles of the tablets coated by aqueous polymer dispersion were investigated by comparing with propranolol hydrochloride osmotic pump tablets coated by an organic solvent. Results showed that the similarity factor (f 2 ) between cellulose acetate-coated tablet and Eudragit-coated tablet was 78.1, and f 2 between cellulose acetate-coated tablet and Kollicoat-coated tablet was 77.6. The linear IVIVC of Eudragit-coated and Kollicoat-coated osmotic pump tablets was determined, which confirmed excellent correlation between the absorption in vivo and the drug release in vitro. Consequently, the membrane coated by aqueous polymer dispersion or organic solvent has similar in vitro release rates of controlled release. Also, compared with organic solvent coating, aqueous polymer dispersion has numerous advantages, such as reduced toxicity and no environmental damage. Therefore, the aqueous polymer dispersion technology has enormous potential as a replacement of organic solvent coating.
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Zero-Valent Metal Emulsion for Reductive Dehalogenation of DNAPLs
NASA Technical Reports Server (NTRS)
Reinhart, Debra R. (Inventor); Clausen, Christian (Inventor); Gelger, Cherie L. (Inventor); Quinn, Jacqueline (Inventor); Brooks, Kathleen (Inventor)
2006-01-01
A zero-valent metal emulsion is used to dehalogenate solvents, such as pooled dense non-aqueous phase liquids (DNAPLs), including trichloroethylene (TCE). The zero-valent metal emulsion contains zero-valent metal particles, a surfactant, oil and water, The preferred zero-valent metal particles are nanoscale and microscale zero-valent iron particles.
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Microwave (MW) irradiation in conjunction with water as reaction media has proven to be a 'greener' chemical approach for expeditious N-alkylation reactions of amines and hydrazines wherein the reactions under mildly basic conditions afford tertiary amines and double N<...
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The gas-phase partitioning tracer method was used to estimate non-aqueous phase liquid (NAPL), water, and air saturations in the vadose zone at a chlorinated-solvent contaminated field site in Tucson, AZ. The tracer test was conducted in a fractured-clay system that is the confin...
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Zero-Valent Metal Emulsion for Reductive Dehalogenation of DNAPLS
NASA Technical Reports Server (NTRS)
Reinhart, Debra R. (Inventor); Clausen, Christian (Inventor); Geiger, Cherie L. (Inventor); Quinn, Jacqueline (Inventor); Brooks, Kathleen (Inventor)
2003-01-01
A zero-valent metal emulsion is used to dehalogenate solvents, such as pooled dense non-aqueous phase liquids (DNAPLs), including trichloroethylene (TCE). The zero-valent metal emulsion contains zero-valent metal particles, a surfactant, oil and water. The preferred zero-valent metal particles are nanoscale and microscale zero-valent iron particles
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Non-aqueous electrolytes for electrochemical cells
Zhang, Zhengcheng; Dong, Jian; Amine, Khalil
2016-06-14
An electrolyte electrochemical device includes an anodic material and an electrolyte, the electrolyte including an organosilicon solvent, a salt, and a hybrid additiving having a first and a second compound, the hybrid additive configured to form a solid electrolyte interphase film on the anodic material upon application of a potential to the electrochemical device.
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NASA Astrophysics Data System (ADS)
Almandoz, M. C.; Sancho, M. I.; Blanco, S. E.
2014-01-01
The solvatochromic behavior of sulfamethoxazole (SMX) was investigated using UV-vis spectroscopy and DFT methods in neat and binary solvent mixtures. The spectral shifts of this solute were correlated with the Kamlet and Taft parameters (α, β and π*). Multiple lineal regression analysis indicates that both specific hydrogen-bond interaction and non specific dipolar interaction play an important role in the position of the absorption maxima in neat solvents. The simulated absorption spectra using TD-DFT methods were in good agreement with the experimental ones. Binary mixtures consist of cyclohexane (Cy)-ethanol (EtOH), acetonitrile (ACN)-dimethylsulfoxide (DMSO), ACN-dimethylformamide (DMF), and aqueous mixtures containing as co-solvents DMSO, ACN, EtOH and MeOH. Index of preferential solvation was calculated as a function of solvent composition and non-ideal characteristics are observed in all binary mixtures. In ACN-DMSO and ACN-DMF mixtures, the results show that the solvents with higher polarity and hydrogen bond donor ability interact preferentially with the solute. In binary mixtures containing water, the SMX molecules are solvated by the organic co-solvent (DMSO or EtOH) over the whole composition range. Synergistic effect is observed in the case of ACN-H2O and MeOH-H2O, indicating that at certain concentrations solvents interact to form association complexes, which should be more polar than the individual solvents of the mixture.
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Dai, Liping; Cheng, Jing; Matsadiq, Guzalnur; Liu, Lu; Li, Jun-Kai
2010-08-03
In the proposed method, an extraction solvent with a lower toxicity and density than the solvents typically used in dispersive liquid-liquid microextraction was used to extract seven polychlorinated biphenyls (PCBs) from aqueous samples. Due to the density and melting point of the extraction solvent, the extract which forms a layer on top of aqueous sample can be collected by solidifying it at low temperatures, which form a layer on top of the aqueous sample. Furthermore, the solidified phase can be easily removed from the aqueous phase. Based on preliminary studies, 1-undecanol was selected as the extraction solvent, and a series of parameters that affect the extraction efficiency were systematically investigated. Under the optimized conditions, enrichment factors for PCBs ranged between 494 and 606. Based on a signal-to-noise ratio of 3, the limit of detection for the method ranged between 3.3 and 5.4 ng L(-1). Good linearity, reproducibility and recovery were also obtained. 2010 Elsevier B.V. All rights reserved.
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SEPARATION OF RUTHENIUM FROM AQUEOUS SOLUTIONS
Callis, C.F.; Moore, R.L.
1959-09-01
>The separation of ruthenium from aqueous solutions containing uranium plutonium, ruthenium, and fission products is described. The separation is accomplished by providing a nitric acid solution of plutonium, uranium, ruthenium, and fission products, oxidizing plutonium to the hexavalent state with sodium dichromate, contacting the solution with a water-immiscible organic solvent, such as hexone, to extract plutonyl, uranyl, ruthenium, and fission products, reducing with sodium ferrite the plutonyl in the solvent phase to trivalent plutonium, reextracting from the solvent phase the trivalent plutonium, ruthenium, and some fission products with an aqueous solution containing a salting out agent, introducing ozone into the aqueous acid solution to oxidize plutonium to the hexavalent state and ruthenium to ruthenium tetraoxide, and volatizing off the ruthenium tetraoxide.
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Process for extracting technetium from alkaline solutions
Moyer, Bruce A.; Sachleben, Richard A.; Bonnesen, Peter V.
1995-01-01
A process for extracting technetium values from an aqueous alkaline solution containing at least one alkali metal hydroxide and at least one alkali metal nitrate, the at least one alkali metal nitrate having a concentration of from about 0.1 to 6 molar. The solution is contacted with a solvent consisting of a crown ether in a diluent for a period of time sufficient to selectively extract the technetium values from the aqueous alkaline solution. The solvent containing the technetium values is separated from the aqueous alkaline solution and the technetium values are stripped from the solvent.
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Mazzini, Virginia; Craig, Vincent S J
2017-10-01
The importance of electrolyte solutions cannot be overstated. Beyond the ionic strength of electrolyte solutions the specific nature of the ions present is vital in controlling a host of properties. Therefore ion specificity is fundamentally important in physical chemistry, engineering and biology. The observation that the strengths of the effect of ions often follows well established series suggests that a single predictive and quantitative description of specific-ion effects covering a wide range of systems is possible. Such a theory would revolutionise applications of physical chemistry from polymer precipitation to drug design. Current approaches to understanding specific-ion effects involve consideration of the ions themselves, the solvent and relevant interfaces and the interactions between them. Here we investigate the specific-ion effects trends of standard partial molar volumes and electrostrictive volumes of electrolytes in water and eleven non-aqueous solvents. We choose these measures as they relate to bulk properties at infinite dilution, therefore they are the simplest electrolyte systems. This is done to test the hypothesis that the ions alone exhibit a specific-ion effect series that is independent of the solvent and unrelated to surface properties. The specific-ion effects trends of standard partial molar volumes and normalised electrostrictive volumes examined in this work show a fundamental ion-specific series that is reproduced across the solvents, which is the Hofmeister series for anions and the reverse lyotropic series for cations, supporting the hypothesis. This outcome is important in demonstrating that ion specificity is observed at infinite dilution and demonstrates that the complexity observed in the manifestation of specific-ion effects in a very wide range of systems is due to perturbations of solvent, surfaces and concentration on the underlying fundamental series. This knowledge will guide a general understanding of specific-ion effects and assist in the development of a quantitative predictive theory of ion specificity.
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NASA Astrophysics Data System (ADS)
Khan, Saleem Nawaz; Hailegiorgis, Sintayehu Mekuria; Man, Zakaria; Shariff, Azmi Mohd
2017-10-01
In this study, the solubility of carbon dioxide (CO2) in the aqueous solution of piperazine (PZ) activated N-methyldiethanolamine (MDEA) was investigated. In the aqueous solution the concentrations of the N-methyldiethanolamine (MDEA) and piperazine (PZ) were kept constant at 30 wt. % and 3 wt. %, respectively. The solubility experiments were carried out between the temperatures ranges of 303.15 to 333.15 K. The pressure range was selected as 2-50 bar for solubility of carbon dioxide in the aqueous solution. The solubility of the CO2 is reported in terms of CO2 loading capacity of the solvent. The loading capacity of the solvent is the ratio between the numbers of moles of CO2 absorbed to the numbers of moles of solvent used. The experimental data showed that the CO2 loading increased with increase in CO2 partial pressure, while it decreased with increase in system's temperature. It was also observed from the experimental data that the higher pressure favors the absorption process while the increased temperature hinders the absorption process of CO2 capture. The loading capacity of the investigated solvent was compared with the loading capacity of the solvents reported in the literature. The investigated solvent showed better solubility in terms of loading capacity.
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REPLACING SOLVENT CLEANING WITH AQUEOUS CLEANING
The report documents actions taken by Robert Bosch Corp., Charleston, SC, in replacing the cleaning solvents 1, 1, 2- trichloro-1, 2, 2-trifluoroethane (CFC-113) and trichloroethylene (TCE) with aqueous solutions. Bosch has succeeded in eliminating all their CFC-113 use and so f...
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Maddi, Balakrishna; Panisko, Ellen; Albrecht, Karl; Howe, Daniel
2016-01-01
Two-dimensional gas chromatography coupled with time-of-flight mass spectrometry is a powerful tool for identifying and quantifying chemical components in complex mixtures. It is often used to analyze gasoline, jet fuel, diesel, bio-diesel and the organic fraction of bio-crude/bio-oil. In most of those analyses, the first dimension of separation is non-polar, followed by a polar separation. The aqueous fractions of bio-crude and other aqueous samples from biofuels production have been examined with similar column combinations. However, sample preparation techniques such as derivatization, solvent extraction, and solid-phase extraction were necessaryprior to analysis. In this study, aqueous fractions obtained from the hydrothermal liquefaction of algae were characterized by two-dimensional gas chromatography coupled with time-of-flight mass spectrometry without prior sample preparation techniques using a polar separation in the first dimension followed by a non-polar separation in the second. Two-dimensional plots from this analysis were compared with those obtained from the more traditional column configuration. Results from qualitative characterization of the aqueous fractions of algal bio-crude are discussed in detail. The advantages of using a polar separation followed by a non-polar separation for characterization of organics in aqueous samples by two-dimensional gas chromatography coupled with time-of-flight mass spectrometry are highlighted. PMID:27022829
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Maddi, Balakrishna; Panisko, Ellen; Albrecht, Karl; Howe, Daniel
2016-03-06
Two-dimensional gas chromatography coupled with time-of-flight mass spectrometry is a powerful tool for identifying and quantifying chemical components in complex mixtures. It is often used to analyze gasoline, jet fuel, diesel, bio-diesel and the organic fraction of bio-crude/bio-oil. In most of those analyses, the first dimension of separation is non-polar, followed by a polar separation. The aqueous fractions of bio-crude and other aqueous samples from biofuels production have been examined with similar column combinations. However, sample preparation techniques such as derivatization, solvent extraction, and solid-phase extraction were necessary prior to analysis. In this study, aqueous fractions obtained from the hydrothermal liquefaction of algae were characterized by two-dimensional gas chromatography coupled with time-of-flight mass spectrometry without prior sample preparation techniques using a polar separation in the first dimension followed by a non-polar separation in the second. Two-dimensional plots from this analysis were compared with those obtained from the more traditional column configuration. Results from qualitative characterization of the aqueous fractions of algal bio-crude are discussed in detail. The advantages of using a polar separation followed by a non-polar separation for characterization of organics in aqueous samples by two-dimensional gas chromatography coupled with time-of-flight mass spectrometry are highlighted.
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NASA Astrophysics Data System (ADS)
Rubinstein, Alexander; Sabirianov, Renat
2011-03-01
Using a non-local electrostatic approach that incorporates the short-range structure of the contacting media, we evaluated the electrostatic contribution to the energy of the complex formation of two model proteins. In this study, we have demonstrated that the existence of an low-dielectric interfacial water layer at the protein-solvent interface reduces the charging energy of the proteins in the aqueous solvent, and consequently increases the electrostatic contribution to the protein binding (change in free energy upon the complex formation of two proteins). This is in contrast with the finding of the continuum electrostatic model, which suggests that electrostatic interactions are not strong enough to compensate for the unfavorable desolvation effects.
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SOLVENT EXTRACTION OF RUTHENIUM
Hyman, H.H.; Leader, G.R.
1959-07-14
The separation of rathenium from aqueous solutions by solvent extraction is described. According to the invention, a nitrite selected from the group consisting of alkali nitrite and alkaline earth nitrite in an equimolecular quantity with regard to the quantity of rathenium present is added to an aqueous solution containing ruthenium tetrantrate to form a ruthenium complex. Adding an organic solvent such as ethyl ether to the resulting mixture selectively extracts the rathenium complex.
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NASA Astrophysics Data System (ADS)
Sukhanov, P. T.; Chibisova, T. V.; Korenman, Ya. I.
2014-12-01
The extraction of local anesthetics from aqueous media with mixtures of solvent is examined and its synergistic and antagonistic effects are determined. Synergism parameters, separation factors, constants for the formation of anesthetic complexes, and solvate numbers are calculated.
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Guo, Mengzhe; Liang, Junling; Wu, Shihua
2010-08-13
In this work, we have developed a novel hybrid two-dimensional counter-current chromatography and liquid chromatography (2D CCC x LC) system for the continuous purification of arctiin from crude extract of Arctium lappa. The first dimensional CCC column has been designed to fractionalize crude complex extract into pure arctiin effluent using a one-component organic/salt-containing system, and the second dimensional LC column has been packed with macroporous resin for on-line adsorption, desalination and desorption of arctiin which was effluent purified from the first CCC dimension. Thus, the crude arctiin mixture has been purified efficiently and conveniently by on-line CCC x LC in spite of the use of a salt-containing solvent system in CCC separation. As a result, high purity (more than 97%) of arctiin has been isolated by repeated injections both using the ethyl acetate-8% sodium chloride aqueous solution and butanol-1% sodium chloride aqueous solution. By contrast with the traditional CCC processes using multi-component organic/aqueous solvent systems, the present on-line CCC x LC process only used a one-component organic solvent and thus the solvent is easier to recover and regenerate. All of used solvents such as ethyl acetate, n-butanol and NaCl aqueous solution are low toxicity and environment-friendly. Moreover, the lower phase of salt-containing aqueous solution used as mobile phase, only contained minor organic solvent, which will save much organic solvent in continuous separation. In summary, our results indicated that the on-line hybrid 2D CCC x LC system using one-component organic/salt-containing aqueous solution is very promising and powerful tool for high-throughput purification of arctiin from fruits of A. lappa. 2010 Elsevier B.V. All rights reserved.
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Tedder, Daniel W.
1985-05-14
Alcohol substantially free of water is prepared by continuously fermenting a fermentable biomass feedstock in a fermentation unit, thereby forming an aqueous fermentation liquor containing alcohol and microorganisms. Continuously extracting a portion of alcohol from said fermentation liquor with an organic solvent system containing an extractant for said alcohol, thereby forming an alcohol-organic solvent extract phase and an aqueous raffinate. Said alcohol is separated from said alcohol-organic solvent phase. A raffinate comprising microorganisms and unextracted alcohol is returned to the fermentation unit.
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NASA Astrophysics Data System (ADS)
Cox, Courtney E.; Phifer, Jeremy R.; Ferreira da Silva, Larissa; Gonçalves Nogueira, Gabriel; Ley, Ryan T.; O'Loughlin, Elizabeth J.; Pereira Barbosa, Ana Karolyne; Rygelski, Brett T.; Paluch, Andrew S.
2017-02-01
Solubility parameter based methods have long been a valuable tool for solvent formulation and selection. Of these methods, the MOdified Separation of Cohesive Energy Density (MOSCED) has recently been shown to correlate well the equilibrium solubility of multifunctional non-electrolyte solids. However, before it can be applied to a novel solute, a limited amount of reference solubility data is required to regress the necessary MOSCED parameters. Here we demonstrate for the solutes methylparaben, ethylparaben, propylparaben, butylparaben, lidocaine and ephedrine how conventional molecular simulation free energy calculations or electronic structure calculations in a continuum solvent, here the SMD or SM8 solvation model, can instead be used to generate the necessary reference data, resulting in a predictive flavor of MOSCED. Adopting the melting point temperature and enthalpy of fusion of these compounds from experiment, we are able to predict equilibrium solubilities. We find the method is able to well correlate the (mole fraction) equilibrium solubility in non-aqueous solvents over four orders of magnitude with good quantitative agreement.
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Cox, Courtney E; Phifer, Jeremy R; Ferreira da Silva, Larissa; Gonçalves Nogueira, Gabriel; Ley, Ryan T; O'Loughlin, Elizabeth J; Pereira Barbosa, Ana Karolyne; Rygelski, Brett T; Paluch, Andrew S
2017-02-01
Solubility parameter based methods have long been a valuable tool for solvent formulation and selection. Of these methods, the MOdified Separation of Cohesive Energy Density (MOSCED) has recently been shown to correlate well the equilibrium solubility of multifunctional non-electrolyte solids. However, before it can be applied to a novel solute, a limited amount of reference solubility data is required to regress the necessary MOSCED parameters. Here we demonstrate for the solutes methylparaben, ethylparaben, propylparaben, butylparaben, lidocaine and ephedrine how conventional molecular simulation free energy calculations or electronic structure calculations in a continuum solvent, here the SMD or SM8 solvation model, can instead be used to generate the necessary reference data, resulting in a predictive flavor of MOSCED. Adopting the melting point temperature and enthalpy of fusion of these compounds from experiment, we are able to predict equilibrium solubilities. We find the method is able to well correlate the (mole fraction) equilibrium solubility in non-aqueous solvents over four orders of magnitude with good quantitative agreement.
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Foams for barriers and nonlethal weapons
NASA Astrophysics Data System (ADS)
Rand, Peter B.
1997-01-01
Our times demand better solutions to conflict resolution than simply shooting someone. Because of this, police and military interest in non-lethal concepts is high. Already in use are pepper sprays, bean-bag guns, flash-bang grenades, and rubber bullets. At Sandia we got a head start on non- lethal weapon concepts. Protection of nuclear materials required systems that went way beyond the traditional back vault. Dispensable deterrents were used to allow a graduated response to a threat. Sticky foams and stabilized aqueous foams were developed to provide access delay. Foams won out for security systems simply because you could get a large volume from a small container. For polymeric foams the expansion ratio is thirty to fifty to one. In aqueous foams expansion ratios of one thousand to ne are easily obtained. Recent development work on sticky foams has included a changeover to environmentally friendly solvents, foams with very low toxicity, and the development of non-flammable silicone resin based foams. High expansion aqueous foams are useful visual and aural obscurants. Our recent aqueous foam development has concentrated on using very low toxicity foaming agents combined with oleoresin capsicum irritant to provide a safe but highly irritating foam.
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Solutions Remediate Contaminated Groundwater
NASA Technical Reports Server (NTRS)
2010-01-01
During the Apollo Program, NASA workers used chlorinated solvents to clean rocket engine components at launch sites. These solvents, known as dense non-aqueous phase liquids, had contaminated launch facilities to the point of near-irreparability. Dr. Jacqueline Quinn and Dr. Kathleen Brooks Loftin of Kennedy Space Center partnered with researchers from the University of Central Florida's chemistry and engineering programs to develop technology capable of remediating the area without great cost or further environmental damage. They called the new invention Emulsified Zero-Valent Iron (EZVI). The groundwater remediation compound is cleaning up polluted areas all around the world and is, to date, NASA's most licensed technology.
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Chemically modified graphite for electrochemical cells
Greinke, R.A.; Lewis, I.C.
1998-05-26
This invention relates to chemically modified graphite particles: (a) that are useful in alkali metal-containing electrode of a electrochemical cell comprising: (1) the electrode, (2) a non-aqueous electrolytic solution comprising an organic aprotic solvent which solvent tends to decompose when the electrochemical cell is in use, and an electrically conductive salt of an alkali metal, and (3) a counter electrode; and (b) that are chemically modified with fluorine, chlorine, iodine or phosphorus to reduce such decomposition. This invention also relates to electrodes comprising such chemically modified graphite and a binder and to electrochemical cells containing such electrodes. 3 figs.
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Chemically modified graphite for electrochemical cells
Greinke, Ronald Alfred; Lewis, Irwin Charles
1998-01-01
This invention relates to chemically modified graphite particles: (a) that are useful in alkali metal-containing electrode of a electrochemical cell comprising: (i) the electrode, (ii) a non-aqueous electrolytic solution comprising an organic aprotic solvent which solvent tends to decompose when the electrochemical cell is in use, and an electrically conductive salt of an alkali metal, and (iii) a counterelectrode; and (b) that are chemically modified with fluorine, chlorine, iodine or phosphorus to reduce such decomposition. This invention also relates to electrodes comprising such chemically modified graphite and a binder and to electrochemical cells containing such electrodes.
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Jain, Rohit; Wu, Zimei; Bork, Olaf; Tucker, Ian G
2012-01-01
Penethamate (PNT) is a diethylaminoethyl ester prodrug of benzylpenicillin used to treat bovine mastitis via the intramuscular route. Because of its instability, PNT products must be reconstituted before administration and the reconstituted injection has a short shelf life (7 days at 2-8°C). The purpose of this paper was to investigate whether the stability of PNT can be improved in order to achieve a chemically stable ready-to-use aqueous-based PNT formulation or at least to extend the shelf life of the reconstituted suspension. A chemical stability study of PNT in aqueous-based solutions as a function of pH, buffer strength, solvent mixtures and temperature, supported by studies of its solubility in mixed solvents, allowed predictions of the shelf life of PNT solution and suspension formulations. PNT degraded in aqueous solutions by several pathways over the pH range 2.0-9.3 with a V-shaped pH-rate profile and a minimum pH of around 4.5. The stability of PNT solutions in mixed solvents was greater than in aqueous solutions. For example, in propylene glycol:citrate buffer (60:40, v/v, pH 4.5), the half-life of PNT was 4.3 days compared with 1.8 days in aqueous buffer. However, solubility of PNT in the mixed solvent was higher than that in aqueous solution and this had an adverse effect on the stability of suspensions. By judicious choosing of pH and mixed solvent, it is possible to achieve a storage life of a PNT suspension of 5.5 months at 5°C, not sufficient for a ready-to-use product but a dramatic improvement in the storage life of the reconstituted product.
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NASA Astrophysics Data System (ADS)
Roy, Mahendra Nath; Roy, Milan Chandra; Basak, Saptarshi
2014-05-01
Qualitative and quantitative analysis of molecular interaction prevailing in glycine, l-alanine, l-valine, and aqueous solution of ionic liquid (IL) [1-ethylpyridinium tetrafluoroborate (] have been investigated by thermophysical properties. The apparent molar volume (), viscosity -coefficient, molal refraction (), and adiabatic compressibility ( of glycine, l-alanine, and l-valine have been studied in 0.001 mol , 0.003 mol , and 0.005 mol aqueous 1-ethylpyridinium tetrafluoroborate [] solutions at 298.15 K from the values of densities , viscosities (), refractive index (, and speed of sound , respectively. The extent of interaction, i.e., the solute-solvent interaction is expressed in terms of the limiting apparent molar volume (, viscosity -coefficient, and limiting apparent molar adiabatic compressibility (. The limiting apparent molar volumes (, experimental slopes ( derived from the Masson equation, and viscosity - and -coefficients using the Jones-Dole equation have been interpreted in terms of ion-ion and ion-solvent interactions, respectively. Molal refractions ( have been calculated with the help of the Lorentz-Lorenz equation. The role of the solvent (aqueous IL solution) and the contribution of solute-solute and solute-solvent interactions to the solution complexes have also been analyzed through the derived properties.
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Separation of switchgrass bio-oil by water/organic solvent addition and pH adjustment
Park, Lydia Kyoung-Eun; Ren, Shoujie; Yiacoumi, Sotira; ...
2016-01-29
Applications of bio-oil are limited by its challenging properties including high moisture content, low pH, high viscosity, high oxygen content, and low heating value. Separation of switchgrass bio-oil components by adding water, organic solvents (hexadecane and octane), and sodium hydroxide may help to overcome these issues. Acetic acid and phenolic compounds were extracted in aqueous and organic phases, respectively. Polar chemicals, such as acetic acid, did not partition in the organic solvent phase. Acetic acid in the aqueous phase after extraction is beneficial for a microbial-electrolysis-cell application to produce hydrogen as an energy source for further hydrodeoxygenation of bio-oil. Organicmore » solvents extracted more chemicals from bio-oil in combined than in sequential extraction; however, organic solvents partitioned into the aqueous phase in combined extraction. When sodium hydroxide was added to adjust the pH of aqueous bio-oil, organic-phase precipitation occurred. As the pH was increased, a biphasic aqueous/organic dispersion was formed, and phase separation was optimized at approximately pH 6. The neutralized organic bio-oil had approximately 37% less oxygen and 100% increased heating value than the initial centrifuged bio-oil. In conclusion, the less oxygen content and increased heating value indicated a significant improvement of the bio-oil quality through neutralization.« less
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Separation of switchgrass bio-oil by water/organic solvent addition and pH adjustment
DOE Office of Scientific and Technical Information (OSTI.GOV)
Park, Lydia Kyoung-Eun; Ren, Shoujie; Yiacoumi, Sotira
Applications of bio-oil are limited by its challenging properties including high moisture content, low pH, high viscosity, high oxygen content, and low heating value. Separation of switchgrass bio-oil components by adding water, organic solvents (hexadecane and octane), and sodium hydroxide may help to overcome these issues. Acetic acid and phenolic compounds were extracted in aqueous and organic phases, respectively. Polar chemicals, such as acetic acid, did not partition in the organic solvent phase. Acetic acid in the aqueous phase after extraction is beneficial for a microbial-electrolysis-cell application to produce hydrogen as an energy source for further hydrodeoxygenation of bio-oil. Organicmore » solvents extracted more chemicals from bio-oil in combined than in sequential extraction; however, organic solvents partitioned into the aqueous phase in combined extraction. When sodium hydroxide was added to adjust the pH of aqueous bio-oil, organic-phase precipitation occurred. As the pH was increased, a biphasic aqueous/organic dispersion was formed, and phase separation was optimized at approximately pH 6. The neutralized organic bio-oil had approximately 37% less oxygen and 100% increased heating value than the initial centrifuged bio-oil. In conclusion, the less oxygen content and increased heating value indicated a significant improvement of the bio-oil quality through neutralization.« less
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NASA Astrophysics Data System (ADS)
Hodgson, Lorna; Thompson, Andrew
2012-03-01
This paper presents the results of a non-HMDS (non-silane) adhesion promoter that was used to reduce the zeta potential for very thin (proprietary) polymer on silicon. By reducing the zeta potential, as measured by the minimum sample required to fully coat a wafer, the amount of polymer required to coat silicon substrates was significantly reduced in the manufacture of X-ray windows used for high transmission of low-energy X-rays. Moreover, this approach used aqueous based adhesion promoter described as a cationic surface active agent that has been shown to improve adhesion of photoresists (positive, negative, epoxy [SU8], e-beam and dry film). As well as reducing the amount of polymer required to coat substrates, this aqueous adhesion promoter is nonhazardous, and contains non-volatile solvents.
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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.
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Mashiko, T; Hiraoka, S; Nagashima, U; Tachikawa, M
2017-01-04
Gear-shaped amphiphile molecules (1) recently synthesized by Hiraoka et al. self-assemble into a hexameric structure, nanocubes (1 6 ), in 25% aqueous methanol due to a solvophobic effect. Here we have carried out molecular dynamic simulations to elucidate the stability of these hexameric capsules (1 6 and 2 6 ) in water, 25% aqueous methanol, and methanol. In all solvents, the 1 6 nanocubes are maintained for all trajectories. On the other hand, 2 6 was found to collapse for one trajectory in water and seven trajectories in 25% aqueous methanol. In a pure methanol solvent, 2 6 was found to collapse for all trajectories. The number of collapsed trajectories of 2 6 increased with the amount of methanol in the solvent. We therefore focused on the structure of the π-π stacking between pyridyl groups and the CH-π interactions between the methyl and pyridyl groups within the nanocube. Our study clearly shows the role played by the methanol solvent molecules in the assembly of the nanocube in terms of the substituent and solvent effects at the molecular level, and that these substituent and solvent effects are important for the self-assembly of the nanocubes.
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Separation by solvent extraction
Holt, Jr., Charles H.
1976-04-06
17. A process for separating fission product values from uranium and plutonium values contained in an aqueous solution, comprising adding an oxidizing agent to said solution to secure uranium and plutonium in their hexavalent state; contacting said aqueous solution with a substantially water-immiscible organic solvent while agitating and maintaining the temperature at from -1.degree. to -2.degree. C. until the major part of the water present is frozen; continuously separating a solid ice phase as it is formed; separating a remaining aqueous liquid phase containing fission product values and a solvent phase containing plutonium and uranium values from each other; melting at least the last obtained part of said ice phase and adding it to said separated liquid phase; and treating the resulting liquid with a new supply of solvent whereby it is practically depleted of uranium and plutonium.
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Separation and concentration of lower alcohols from dilute aqueous solutions
Moore, Raymond H.; Eakin, David E.; Baker, Eddie G.; Hallen, Richard T.
1991-01-01
A process for producing, from a dilute aqueous solution of a lower (C.sub.1 -C.sub.5) alcohol, a concentrated liquid solution of the alcohol in an aromatic organic solvent is disclosed. Most of the water is removed from the dilute aqueous solution of alcohol by chilling sufficiently to form ice crystals. Simultaneously, the remaining liquid is extracted at substantially the same low temperature with a liquid organic solvent that is substantially immiscible in aqueous liquids and has an affinity for the alcohol at that temperature, causing the alcohol to transfer to the organic phase. After separating the organic liquid from the ice crystals, the organic liquid can be distilled to enrich the concentration of alcohol therein. Ethanol so separated from water and concentrated in an organic solvent such as toluene is useful as an anti-knock additive for gasoline.
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Biodegradation of Chlorinated Solvents: Reactions near DNAPL and Enzyme Function
DOE Office of Scientific and Technical Information (OSTI.GOV)
McCarty, Perry L.; Spormann, Alfred M.; Criddle, Craig S.
The anaerobic biodegradation of chlorinated solvents is of great interest both for natural attenuation and for engineered remediation of these hazardous contaminants in groundwater. Compounds to be studied are carbon tetrachloride (CT) and the chlorinated ethenes, tetrachloroethene (PCE), trichloroethene (TCE) cis-1,2-dichloroethene (cDCE), and vinyl chloride (VC). The chlorinated solvents often are present as dense non-aqueous-phase liquids (DNAPLs), which are difficult to remove. Biodegradation of DNAPLs was previously thought not possible because of toxicity, but recent evidence indicates that under the right conditions, biodegradation is possible. Anaerobic biodegradation of DNAPLs is the major subject of this research. The specific objectives ofmore » this multi-investigator effort are: (1) Evaluate the potential for chlorinated solvent biodegradation near DNAPLs, (2) Provide a molecular understanding of the biological mechanisms involved, (3) Determine cellular components involved in carbon tetrachloride transformation by Pseudomonas stutzeri strain KC without chloroform formation.« less
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Nonhazardous solvent composition and method for cleaning metal surfaces
Googin, John M.; Simandl, Ronald F.; Thompson, Lisa M.
1993-01-01
A solvent composition for displacing greasy and oily contaminants as well as water and/or aqueous residue from metallic surfaces, especially surfaces of radioactive materials so that such surfaces can be wiped clean of the displaced contaminants, water and/or aqueous residue. The solvent composition consists essentially of a blend of nonpolar aliphatic hydrocarbon solvent having a minimum flash point of about 140.degree. F. and 2 to 25 volume percent of a polar solvent having a flash point sufficiently high so as to provide the solvent composition with a minimum flash point of at least 140.degree. F. The solvent composition is nonhazardous so that when it is used to clean the surfaces of radioactive materials the waste in the form of paper or cloth wipes, lab coats and the like used in the cleaning operation is not considered to be mixed waste composed of a hazardous solvent and a radioactive material.
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Nonhazardous solvent composition and method for cleaning metal surfaces
Googin, J.M.; Simandl, R.F.; Thompson, L.M.
1993-05-04
A solvent composition for displacing greasy and oily contaminants as well as water and/or aqueous residue from metallic surfaces, especially surfaces of radioactive materials so that such surfaces can be wiped clean of the displaced contaminants, water and/or aqueous residue. The solvent composition consists essentially of a blend of nonpolar aliphatic hydrocarbon solvent having a minimum flash point of about 140 F and 2 to 25 volume percent of a polar solvent having a flash point sufficiently high so as to provide the solvent composition with a minimum flash point of at least 140 F. The solvent composition is nonhazardous so that when it is used to clean the surfaces of radioactive materials the waste in the form of paper or cloth wipes, lab coats and the like used in the cleaning operation is not considered to be mixed waste composed of a hazardous solvent and a radioactive material.
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Solvation thermodynamics of L-cystine, L-tyrosine, and L-leucine in aqueous-electrolyte media
NASA Astrophysics Data System (ADS)
Roy, Sanjay; Guin, Partha Sarathi; Mahali, Kalachand; Dolui, Bijoy Krishna
2017-12-01
Solubilities of L-cystine, L-tyrosine, and L-leucine in aqueous NaCl media at 298.15 K have been studied. Indispensable and related solvent parameters such as molar mass, molar volume, etc., were also determined. The results are used to evaluate the standard transfer Gibbs free energy, cavity forming enthalpy of transfer, cavity forming transfer Gibbs free energy and dipole-dipole interaction effects during the course of solvation. Various weak interactions involving solute-solvent or solvent-solvent molecules were characterized in order to find their role on the solvation of these amino acids.
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Solvatochromic fluorescence characteristics of cinnamoyl pyrone derivatives
NASA Astrophysics Data System (ADS)
Benosmane, Nadjib; Boutemeur, Baya; Hamdi, Safouane M.; Hamdi, Maamar; Silva, Artur S. M.
2017-12-01
The solvatochromic fluorescence behavior of cinnamoyl pyrone derivatives has been studied in several polar and non-polar solvents. The fluorescence spectra of these compounds exhibit red shift from its absorption spectra and present an excellent correlation with solvent polarity. Cinnamoyl pyrones show a significant spectral shift in fluorescence emission as a function of water composition in binary aqueous solutions mixture. This change is due to the specific intermolecular hydrogen bonding of cinnamoyl pyrones with a molecules of water, due to the deactivation of the lowest excited singlet state of these compounds. The relative quantum yields are calculated. It is found that the quantum yields of the cinnamoyl pyrones vary with the change in the solvent polarity indicating the dependency of fluorescence properties on the solvent nature. It has been observed that the addition of water and pH medium can affect the fluorescence properties of cinnamoyl pyrones in ethanol. This study exhibited that due to the solvent sensitive emission, cinnamoyl pyrone derivatives are a good compound to be used as fluorescence probes.
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Fabrication of ionic liquid electrodeposited Cu--Sn--Zn--S--Se thin films and method of making
Bhattacharya, Raghu Nath
2016-01-12
A semiconductor thin-film and method for producing a semiconductor thin-films comprising a metallic salt, an ionic compound in a non-aqueous solution mixed with a solvent and processing the stacked layer in chalcogen that results in a CZTS/CZTSS thin films that may be deposited on a substrate is disclosed.
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Lee, Sang-Joon; Park, Sung Soo; Lee, Sang Hyun; Hong, Sang-Hyun; Ha, Chang-Sik
2013-11-01
Transparent mesoporous silica plates doped with rare-earth metal oxide were prepared using solvent-evaporation method based on the self-organization between structure-directing agent and silicate in a non-aqueous solvent. A triblock copolymer, Pluronic (F127 or P123), was used as the structure-directing agent, while tetraethyl orthosilicate (TEOS) was used as a silica source. The pore diameter and the surface area of the mesoporous silica plate prepared with the optimized conditions were ca 40 A and 600 m2 g(-1), respectively, for both structure-directing agent. Rare-earth metal oxides (Eu, Tb, Tm oxide) in mesochannel were formed via one-step synthetic route based on the preparation method of a silica plate. Optical properties of rare-earth metal oxide-doped mesoporous silica plates were investigated by UV irradiation and photoluminescence (PL) spectroscopy. Under the exitation wavelength of 254 nm, the doped mesoporous silica plates emitted red, green and blue for Eu, Tb and Tm oxides, respectively. Rare-earth metal oxide-doped mesoporous silica plates showed enhanced PL intensity compared to that of the bulk rare-earth metal oxide.
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SALICYLATE PROCESS FOR THORIUM SEPARATION FROM RARE EARTHS
Cowan, G.A.
1959-08-25
The separation of thorium from rare earths is accomplished by forming an aqueous solution of salts of thorium and rare earths and sufficient acetate buffer to provide a pH of between 2 and 5, adding an ammonium salicylate to the aqueous buffered solution, contacting the resultant solution with a substantially water-immiscible organic solvent mixture of an ether and an ester, and separating the solvent extract phase containing thorium salicylate from the aqueous phase containing the rare earths.
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Solvent-Ion Interactions in Salt Water: A Simple Experiment.
ERIC Educational Resources Information Center
Willey, Joan D.
1984-01-01
Describes a procedurally quick, simple, and inexpensive experiment which illustrates the magnitude and some effects of solvent-ion interactions in aqueous solutions. Theoretical information, procedures, and examples of temperature, volume and hydration number calculations are provided. (JN)
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The effect of deep eutectic solvents on catalytic function and structure of bovine liver catalase.
Harifi-Mood, Ali Reza; Ghobadi, Roohollah; Divsalar, Adeleh
2017-02-01
Aqueous solutions of reline and glyceline, the most common deep eutectic solvents, were used as a medium for Catalase reaction. By some spectroscopic methods such as UV-vis, fluorescence and circular dichroism (CD) function and structure of Catalase were investigated in aqueous solutions of reline and glyceline. These studies showed that the binding affinity of the substrate to the enzyme increased in the presence of 100mM glyceline solution, which contrasts with reline solution that probably relates to instructive changes in secondary structure of protein. Meanwhile, enzyme remained nearly 70% and 80% active in this concentration of glyceline and reline solutions respectively. In the high concentration of DES solutions, enzyme became mainly inactive but surprisingly stayed in nearly 40% active in choline chloride solution, which is the common ion species in reline and glyceline solvents. It is proposed that the chaotropic nature of choline cation might stop the reducing trend of activity in concentrated choline chloride solutions but this instructive effect is lost in aqueous deep eutectic solvents. In this regard, the presence of various concentrations of deep eutectic solvents in the aqueous media of human cells would be an activity adjuster for this important enzyme in its different operation conditions. Copyright © 2016 Elsevier B.V. All rights reserved.
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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.
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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.
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Nanocellular foam with solid flame retardant
DOE Office of Scientific and Technical Information (OSTI.GOV)
Chen, Liang; Kelly-Rowley, Anne M.; Bunker, Shana P.
Prepare nanofoam by (a) providing an aqueous solution of a flame retardant dissolved in an aqueous solvent, wherein the flame retardant is a solid at 23.degree. C. and 101 kiloPascals pressure when in neat form; (b) providing a fluid polymer composition selected from a solution of polymer dissolved in a water-miscible solvent or a latex of polymer particles in a continuous aqueous phase; (c) mixing the aqueous solution of flame retardant with the fluid polymer composition to form a mixture; (d) removing water and, if present, solvent from the mixture to produce a polymeric composition having less than 74 weight-percentmore » flame retardant based on total polymeric composition weight; (e) compound the polymeric composition with a matrix polymer to form a matrix polymer composition; and (f) foam the matrix polymer composition into nanofoam having a porosity of at least 60 percent.« less
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Weissenberg, M; Schaeffler, I; Menagem, E; Barzilai, M; Levy, A
1997-01-03
A simple, rapid high-performance liquid chromatography method has been devised in order to separate and quantify the xanthophylls capsorubin and capasanthin present in red pepper (Capsicum annuum L.) fruits and preparations made from them (paprika and oleoresin). A reversed-phase isocratic non-aqueous system allows the separation of xanthophylls within a few minutes, with detection at 450 nm, using methyl red as internal standard to locate the various carotenoids and xanthophylls found in plant extracts. The selection of extraction solvents, mild saponification conditions, and chromatographic features is evaluated and discussed. The method is proposed for rapid screening of large plant populations, plant selection, as well as for paprika products and oleoresin, and also for nutrition and quality control studies.
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SOLVENT EXTRACTION PROCESS FOR PLUTONIUM
Seaborg, G.T.
1959-04-14
The separation of plutonium from aqueous inorganic acid solutions by the use of a water immiscible organic extractant liquid is described. The plutonium must be in the oxidized state, and the solvents covered by the patent include nitromethane, nitroethane, nitropropane, and nitrobenzene. The use of a salting out agents such as ammonium nitrate in the case of an aqueous nitric acid solution is advantageous. After contacting the aqueous solution with the organic extractant, the resulting extract and raffinate phases are separated. The plutonium may be recovered by any suitable method.
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Solvent Extraction of Furfural From Biomass
NASA Technical Reports Server (NTRS)
Humphrey, M. F.
1984-01-01
Solvent-extraction method reduces energy required to remove furfural produced during acid hydrolysis of biomass. Acid hydrolysis performed in vessel containing both solvents and reacting ingredients. With intimate contact between solvents and aqueous hydrolyis liqour, furfural removed form liquor almost as fast as it forms.
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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.
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Microbial production of epoxides
Clark, Thomas R.; Roberto, Francisco F.
2003-06-10
A method for microbial production of epoxides and other oxygenated products is disclosed. The method uses a biocatalyst of methanotrophic bacteria cultured in a biphasic medium containing a major amount of a non-aqueous polar solvent. Regeneration of reducing equivalents is carried out by using endogenous hydrogenase activity together with supplied hydrogen gas. This method is especially effective with gaseous substrates and cofactors that result in liquid products.
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RECOVERY OF URANIUM BY SECONDARY XANTHATE COMPLEXING
Neville, O.K.
1959-09-01
A method is described for separating and recovering uranium values contained in an acidic aqueous solution together with thorium or protactinium values. In accordance with the invention, the acidic solution containing uranium in the uranyl form is contacted with an organic xanthate. The xanthate forms a urano-xanthate complex but is substantially non-reactive with thorium and protactinium. The urano-xanthate complex is recovered by organic solvent extraction.
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NASA Astrophysics Data System (ADS)
Putschögl, M.; Zirak, P.; Penzkofer, A.
2008-01-01
The absorption and fluorescence behaviour of trans- p-coumaric acid ( trans-4-hydroxycinnamic acid) is investigated in buffered aqueous solution over a wide range from pH 1 to pH 12, in un-buffered water, and in some organic solvents. Absorption cross-section spectra, fluorescence quantum distributions, fluorescence quantum yields, and degrees of fluorescence polarisation are measured. p-Coumaric acid exists in different ionic forms in aqueous solution depending on the pH. There is an equilibrium between the neutral form ( p-CAH 2) and the single anionic form ( p-CAH -) at low pH (p Kna ≈ 4.9), and between the single anionic and the double anionic form ( p-CA 2-) at high pH (p Kaa ≈ 9.35). In the organic solvents studied trans- p-coumaric acid is dissolved in its neutral form. The fluorescence quantum yield of trans- p-coumaric acid in aqueous solution is ϕF ≈ 1.4 × 10 -4 for the neutral and the single anionic form, while it is ϕF ≈ 1.3 × 10 -3 for the double anionic form. For trans- p-coumaric acid in organic solvents fluorescence quantum yields in the range from 4.8 × 10 -5 (acetonitrile) to 1.5 × 10 -4 (glycerol) were measured. The fluorescence spectra are 7700-10,000 cm -1 Stokes shifted in aqueous solution, and 5400-8200 cm -1 Stokes shifted in the studied organic solvents. Decay paths responsible for the low fluorescence quantum yields are discussed (photo-isomerisation and internal conversion for p-CA 2-, solvent-assisted intra-molecular charge-transfer or ππ ∗ to nπ ∗ transfer and internal conversion for p-CAH 2 and p-CAH -). The solvent dependence of the first ππ ∗ electronic transition frequency and of the fluorescence Stokes shift of p-CAH 2 is discussed in terms of polar solute-solvent interaction effects. Thereby the ground-state and excite-state molecular dipole moments are extracted.
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COORDINATION COMPOUND-SOLVENT EXTRACTION PROCESS FOR URANIUM RECOVERY
Reas, W.H.
1959-03-10
A method is presented for the separation of uranium from aqueous solutions containing a uranyl salt and thorium. Thc separation is effected by adding to such solutions an organic complexing agent, and then contacting the solution with an organic solvent in which the organic complexing agent is soluble. By use of the proper complexing agent in the proper concentrations uranium will be complexed and subsequently removed in the organic solvent phase, while the thorium remains in the aqueous phase. Mentioned as suitable organic complexing agents are antipyrine, bromoantipyrine, and pyramidon.
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Farajzadeh, Mir Ali; Mohebbi, Ali; Feriduni, Behruz
2016-05-12
In this study, a rapid, simple, and efficient sample preparation method based on continuous dispersive liquid-liquid microextraction has been developed for the extraction and preconcentration of aryloxyphenoxy-propionate herbicides from aqueous samples prior to their analysis by gas chromatography-flame ionization detection. In this method, two parallel glass tubes with different diameters are connected with a teflon stopcock and used as an extraction device. A mixture of disperser and extraction solvents is transferred into one side (narrow tube) of the extraction device and an aqueous phase containing the analytes is filled into the other side (wide tube). Then the stopcock is opened and the mixture of disperser and extraction solvents mixes with the aqueous phase. By this action, the extraction solvent is dispersed continuously as fine droplets into the aqueous sample and the target analytes are extracted into the fine droplets of the extraction solvent. The fine droplets move up through the aqueous phase due to its low density compared to aqueous phase and collect on the surface of the aqueous phase as an organic layer. Finally an aliquot of the organic phase is removed and injected into the separation system for analysis. Several parameters that can affect extraction efficiency including type and volume of extraction and disperser solvents, sample pH, and ionic strength were investigated and optimized. Under the optimum extraction conditions, the extraction recoveries and enrichment factors ranged from 49 to 74% and 1633 to 2466, respectively. Relative standard deviations were in the ranges of 3-6% (n = 6, C = 30 μg L(-1)) for intra-day and 4-7% (n = 4, C = 30 μg L(-1)) for inter-day precisions. The limits of detection were in the range of 0.20-0.86 μg L(-1). Finally the proposed method was successfully applied to determine the target herbicides in fruit juice and vegetable samples. Copyright © 2016 Elsevier B.V. All rights reserved.
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Strengthening of the Coordination Shell by Counter Ions in Aqueous Th 4+ Solutions
DOE Office of Scientific and Technical Information (OSTI.GOV)
Atta-Fynn, Raymond; Bylaska, Eric J.; de Jong, Wibe A.
The presence of counter ions in solutions containing highly charged metal cations can trigger processes such as ion-pair formation, hydrogen bond breakages and subsequent reformation, and ligand exchanges. In this work, it is shown how halide (Cl-, Br-) and perchlorate (ClO4-) anions affect the strength of the primary solvent coordination shells around Th4+ using explicit solvent and finite temperature ab initio molecular dynamics modeling methods. The 9-fold solvent geometry was found to be the most stable hydration structure in each aqueous solution. Relative to the dilute aqueous solution, the presence of the counter ions did not significantly alter the geometrymore » of the primary hydration shell. However, the free energy analyses indicated that the 10-fold hydrated states were thermodynamically accessible in dilute and bromide aqueous solutions within 1 kcal/mol. Analysis of the results showed that the hydrogen bond lifetimes were longer and solvent exchange energy barriers were larger in solutions with counter ions in comparison with the solution with no counter ions. This implies that the presence of the counter ions induces a strengthening of the Th4+ hydration shell.« less
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2017-01-01
The ability to process conjugated polymers via aqueous solution is highly advantageous for reducing the costs and environmental hazards of large scale roll-to-roll processing of organic electronics. However, maintaining competitive electronic properties while achieving aqueous solubility is difficult for several reasons: (1) Materials with polar functional groups that provide aqueous solubility can be difficult to purify and characterize, (2) many traditional coupling and polymerization reactions cannot be performed in aqueous solution, and (3) ionic groups, though useful for obtaining aqueous solubility, can lead to a loss of solid-state order, as well as a screening of any applied bias. As an alternative, we report a multistage cleavable side chain method that combines desirable aqueous processing attributes without sacrificing semiconducting capabilities. Through the attachment of cleavable side chains, conjugated polymers have for the first time been synthesized, characterized, and purified in organic solvents, converted to a water-soluble form for aqueous processing, and brought through a final treatment to cleave the polymer side chains and leave behind the desired electronic material as a solvent-resistant film. Specifically, we demonstrate an organic soluble polythiophene that is converted to an aqueous soluble polyelectrolyte via hydrolysis. After blade coating from an aqueous solution, UV irradiation is used to cleave the polymer’s side chains, resulting in a solvent-resistant, electroactive polymer thin film. In application, this process results in aqueous printed materials with utility for solid-state charge transport in organic field effect transistors (OFETs), along with red to colorless electrochromism in ionic media for color changing displays, demonstrating its potential as a universal method for aqueous printing in organic electronics. PMID:28979937
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Schmatz, Brian; Yuan, Zhibo; Lang, Augustus W; Hernandez, Jeff L; Reichmanis, Elsa; Reynolds, John R
2017-09-27
The ability to process conjugated polymers via aqueous solution is highly advantageous for reducing the costs and environmental hazards of large scale roll-to-roll processing of organic electronics. However, maintaining competitive electronic properties while achieving aqueous solubility is difficult for several reasons: (1) Materials with polar functional groups that provide aqueous solubility can be difficult to purify and characterize, (2) many traditional coupling and polymerization reactions cannot be performed in aqueous solution, and (3) ionic groups, though useful for obtaining aqueous solubility, can lead to a loss of solid-state order, as well as a screening of any applied bias. As an alternative, we report a multistage cleavable side chain method that combines desirable aqueous processing attributes without sacrificing semiconducting capabilities. Through the attachment of cleavable side chains, conjugated polymers have for the first time been synthesized, characterized, and purified in organic solvents, converted to a water-soluble form for aqueous processing, and brought through a final treatment to cleave the polymer side chains and leave behind the desired electronic material as a solvent-resistant film. Specifically, we demonstrate an organic soluble polythiophene that is converted to an aqueous soluble polyelectrolyte via hydrolysis. After blade coating from an aqueous solution, UV irradiation is used to cleave the polymer's side chains, resulting in a solvent-resistant, electroactive polymer thin film. In application, this process results in aqueous printed materials with utility for solid-state charge transport in organic field effect transistors (OFETs), along with red to colorless electrochromism in ionic media for color changing displays, demonstrating its potential as a universal method for aqueous printing in organic electronics.
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NASA Astrophysics Data System (ADS)
Le, Khai Q.; Dang, Ngo Hai
2018-05-01
This paper investigates solvent and concentration effects on photoluminescence (PL) or fluorescence properties of Rhodamine 800 (Rho800) dyes formed in aqueous solution and polymer thin-film. Various commonly used organic solvents including ethanol, methanol and cyclopentanol were studied at a constant dye concentration. There were small changes in the PL spectra for the different solvents in terms of PL intensity and peak wavelength. The highest PL intensity was observed for cyclopentanol and the lowest for ethanol. The longest peak wavelength was found in cyclopentanol (716 nm) and the shortest in methanol (708 nm). Dissolving the dye powder in the methanol solvent and varying the dye concentration in aqueous solution from the high concentrated solution to highly dilute states, the wavelength tunability was observed between about 700 nm in the dilute state and 730 nm at high concentration. Such a large shift may be attributed to the formation of dye aggregates. Rho800 dye-doped polyvinyl alcohol (PVA) polymer thin-film was further investigated. The PL intensity of the dye in the form of thin-film is lower than that of the aqueous solution form whereas the peak wavelength is redshifted due to the presence of PVA. This paper, to our best knowledge, reports the first study of spectroscopic properties of Rho800 dyes in various forms and provides useful guidelines for production of controllable organic luminescence sources.
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SEPARATION PROCESS FOR TRANSURANIC ELEMENT AND COMPOUNDS THEREOF
Magnusson, L.B.
1958-04-01
A process is described for the separation of neptunium, from aqueous solutions of neptunium, plutonium, uraniunn, and fission prcducts. This separation from an acidic aqueous solution of a tetravalent neptuniunn can be made by contacting the solution with a certain type of chelating,; agent, preferably dissolved in an organic solvent, to form a neptunium chelate compound. When the organic solvent is present, the neptunium chelate compound is extracted; otherwise, it precipitates from the aqueous solution and is separated by any suitable means. The chelating agent is a fluorinated BETA -diketone. such as trifluoroacetyl acetone.
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Effect of solution non-ideality on erythrocyte volume regulation.
Levin, R L; Cravalho, E G; Huggins, C E
1977-03-01
A non-ideal, hydrated, non-dilute pseudo-binary salt-protein-water solution model of the erythrocyte intracellular solution is presented to describe the osmotic behavior of human erythrocytes. Existing experimental activity data for salts and proteins in aqueous solutions are used to formulate van Laar type expressions for the solvent and solute activity coefficients. Reasonable estimates can therefore be made of the non-ideality of the erythrocyte intracellular solution over a wide range of osmolalities. Solution non-ideality is shown to affect significantly the degree of solute polarization within the erythrocyte intracellular solution during freezing. However, the non-ideality has very little effect upon the amount of water retained within erythrocytes cooled at sub-zero temperatures.
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NASA Astrophysics Data System (ADS)
Cai, Yunshen
Electrospinning produces submicron fibers from a wide range of polymer/solvent systems that enable a variety of different applications. In electrospinning process, a straight polymer/solvent charged jet is initially formed, followed by a circular moving jet in the shape of a cone, called the bending region. The process physics in the bending region are difficult to study since the jet diameter cannot be measured directly due to its rapid motion and small size ( microns and smaller), and due to complex coupling of multiple forces, mass transport, and changing jet geometry. Since the solutions studied are hydrophilic, they readily absorb ambient moisture. This thesis explores the role of the bending region in determining the resulting electrospun fiber diameter through a combined experimental and modeling analysis for a variety of hydrophilic polymer/solvent solutions. Electrospinning experiments were conducted over a broad range of operating conditions for 4 different polymer/solvent systems. Comparison of the final straight jet diameters to fiber diameters reveals that between 30% to 60% jet thinning occurs in the bending region. These experiments also reveal that relative humidity significantly affects the electrospinning process and final fiber diameter, even for non-aqueous solutions. A model is developed to obtain insight into the bending region process physics. Important ones include understanding the mass transport for non-aqueous hydrophilic jets (including solvent evaporation and water absorption on the jet surface, radial diffusion, and axial advection), and the coupling between the mass and force balances that determines the final fiber diameter. The absorption and evaporation physics is validated by evaporation experiments. The developed model predicts fiber diameter to within of 8%, even though the solution properties and operating conditions that determines net stretching forces and net evaporation rates vary over a large range. Model analysis reveals how the net evaporation rate affects the jet length and net stretching force, both of which ultimately determine the fiber diameter. It is also shown that the primary impact of RH on the process is through occupation of the surface states that limits solvent evaporation rate, rather than the amount of water absorbed. Correlation functions between process conditions, solution properties and the resulting fiber diameters are discussed.
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Morais, Eduarda S; Mendonça, Patrícia V; Coelho, Jorge F J; Freire, Mara G; Freire, Carmen S R; Coutinho, João A P; Silvestre, Armando J D
2018-02-22
This work contributes to the development of integrated lignocellulosic-based biorefineries by the pioneering exploitation of hardwood xylans by solubilization and extraction in deep eutectic solvents (DES). DES formed by choline chloride and urea or acetic acid were initially evaluated as solvents for commercial xylan as a model compound. The effects of temperature, molar ratio, and concentration of the DES aqueous solutions were evaluated and optimized by using a response surface methodology. The results obtained demonstrated the potential of these solvents, with 328.23 g L -1 of xylan solubilization using 66.7 wt % DES in water at 80 °C. Furthermore, xylans could be recovered by precipitation from the DES aqueous media in yields above 90 %. The detailed characterization of the xylans recovered after solubilization in aqueous DES demonstrated that 4-O-methyl groups were eliminated from the 4-O-methylglucuronic acids moieties and uronic acids (15 %) were cleaved from the xylan backbone during this process. The similar M w values of both pristine and recovered xylans confirmed the success of the reported procedure. DES recovery in four additional extraction cycles was also demonstrated. Finally, the successful extraction of xylans from Eucalyptus globulus wood by using aqueous solutions of DES was demonstrated. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
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NASA Astrophysics Data System (ADS)
Yang, Huachao; Bo, Zheng; Yang, Jinyuan; Yan, Jianhua; Cen, Kefa
2017-10-01
Solid-liquid interactions are considered to play a crucial role in charge storage capability of electric double-layer capacitors (EDLCs). In this work, effects of van der Waals (VDW) strengths on the EDL structures and capacitive performances within two representative electrolytes of solvated aqueous solutions and solvent-free ionic liquids are illuminated by molecular dynamics simulations. Single crystalline metals with similar lattice constant but diverse VDW potentials are employed as electrodes. Upon enhancing VDW strengths, capacitance of aqueous electrolytes first increases conspicuously by ∼34.0% and then descends, manifesting a non-monotonic trend, which goes beyond traditional perspectives. Such unusual observation is interpreted by the excluded-volume effects stemmed from ion-solvent competitions. Stimulated by predominant coulombic interactions, more ions are aggregated at the interface despite of the increasing VDW potentials, facilitating superior screening efficiency and capacitance. However, further enhancing strengths preferentially attracts more solvents instead of ions to the electrified surface, which in turn strikingly repels ions from Helmholtz layers, deteriorating electrode capacitance. An essentially similar feather is also recognized for ionic liquids, while the corresponding mechanisms are prominently ascribed to the suppressed ionic separations issued from cation-anion competitions. We highlight that constructing electrode materials with a moderate-hydrophilicity could further advance the performances of EDLCs.
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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.
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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.
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NASA Astrophysics Data System (ADS)
Pandey, R. B.; Jacobs, D. J.; Farmer, B. L.
2017-05-01
The effect of preferential binding of solute molecules within an aqueous solution on the structure and dynamics of the histone H3.1 protein is examined by a coarse-grained Monte Carlo simulation. The knowledge-based residue-residue and hydropathy-index-based residue-solvent interactions are used as input to analyze a number of local and global physical quantities as a function of the residue-solvent interaction strength (f). Results from simulations that treat the aqueous solution as a homogeneous effective solvent medium are compared to when positional fluctuations of the solute molecules are explicitly considered. While the radius of gyration (Rg) of the protein exhibits a non-monotonic dependence on solvent interaction over a wide range of f within an effective medium, an abrupt collapse in Rg occurs in a narrow range of f when solute molecules rapidly bind to a preferential set of sites on the protein. The structure factor S(q) of the protein with wave vector (q) becomes oscillatory in the collapsed state, which reflects segmental correlations caused by spatial fluctuations in solute-protein binding. Spatial fluctuations in solute binding also modify the effective dimension (D) of the protein in fibrous (D ˜ 1.3), random-coil (D ˜ 1.75), and globular (D ˜ 3) conformational ensembles as the interaction strength increases, which differ from an effective medium with respect to the magnitude of D and the length scale.
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Characterizing Fullerene Nanoparticles in Aqueous Suspensions
Studies have indicated that fullerenes can form stable colloidal suspensions in water when introduced to the aqueous phase through solvent exchange, sonication, or extended mixing. The colloidal suspensions created using these techniques have effective aqueous phase concentratio...
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Ge, Dandan; Zhang, Yi; Dai, Yixiu; Yang, Shumin
2018-04-01
Deep eutectic solvents are considered as new and green solvents that can be widely used in analytical chemistry such as microextraction. In the present work, a new dl-menthol-based hydrophobic deep eutectic solvent was synthesized and used as extraction solvents in an air-assisted dispersive liquid-liquid microextraction method for preconcentration and extraction of benzophenone-type UV filters from aqueous samples followed by high-performance liquid chromatography with diode array detection. In an experiment, the deep eutectic solvent formed by dl-menthol and decanoic acid was added to an aqueous solution containing the UV filters, and then the mixture was sucked up and injected five times by using a glass syringe, and a cloudy state was achieved. After extraction, the solution was centrifuged and the upper phase was subjected to high-performance liquid chromatography for analysis. Various parameters such as the type and volume of the deep eutectic solvent, number of pulling, and pushing cycles, solution pH and salt concentration were investigated and optimized. Under the optimum conditions, the developed method exhibited low limits of detection and limits of quantitation, good linearity, and precision. Finally, the proposed method was successfully applied to determine the benzophenone-type filters in environmental water samples with relative recoveries of 88.8-105.9%. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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NASA Astrophysics Data System (ADS)
Shin, Dongkyun; Hong, Ki-Young; Park, Jongwoon
2017-12-01
Due to capillary rise, organic thin films fabricated by solution coating exhibit the concave thickness profile. It is found that the thickness and emission uniformities within pixels vary depending sensitively on the pre-drying treatment that has been done before hard bake. We investigate its effect on the film quality by varying the temperature, time, pressure, fluid flow-related solute concentration, and evaporation-related solvent. To this end, we carry out spin coatings of a non-aqueous poly(N-vinylcarbazole) (PVK) for a hole transporting blanket layer. With a low-boiling-point (BP) organic solvent, the pre-drying makes no significant impact on the thickness profiles. With a high-BP organic solvent, the PVK films pre-dried in a vacuum for a sufficient time exhibit very uniform light emission in the central region, but non-emission phenomenon near the perimeter of pixels. It is addressed that such a non-emission phenomenon can be suppressed to some extent by decreasing the vacuum pressure. However, the rapid evaporation by heat conduction during the pre-drying degrades the thickness uniformity due to a rapid microflow of solute from the edge to the center. No further enhancement in the thickness uniformity is obtained by varying the solute concentration and using a mixture of low- and high-BP solvents.
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Non-ideality by sedimentation velocity of halophilic malate dehydrogenase in complex solvents.
Solovyova, A; Schuck, P; Costenaro, L; Ebel, C
2001-01-01
We have investigated the potential of sedimentation velocity analytical ultracentrifugation for the measurement of the second virial coefficients of proteins, with the goal of developing a method that allows efficient screening of different solvent conditions. This may be useful for the study of protein crystallization. Macromolecular concentration distributions were modeled using the Lamm equation with the approximation of linear concentration dependencies of the diffusion constant, D = D(o) (1 + k(D)c), and the reciprocal sedimentation coefficient s = s(o)/(1 + k(s)c). We have studied model distributions for their information content with respect to the particle and its non-ideal behavior, developed a strategy for their analysis by direct boundary modeling, and applied it to data from sedimentation velocity experiments on halophilic malate dehydrogenase in complex aqueous solvents containing sodium chloride and 2-methyl-2,4-pentanediol, including conditions near phase separation. Using global modeling for three sets of data obtained at three different protein concentrations, very good estimates for k(s) and s degrees and also for D degrees and the buoyant molar mass were obtained. It was also possible to obtain good estimates for k(D) and the second virial coefficients. Modeling of sedimentation velocity profiles with the non-ideal Lamm equation appears as a good technique to investigate weak inter-particle interactions in complex solvents and also to extrapolate the ideal behavior of the particle. PMID:11566761
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Thermodynamic constrains for life based on non-aqueous polar solvents on free-floating planets.
Badescu, Viorel
2011-02-01
Free-floating planets (FFPs) might originate either around a star or in solitary fashion. These bodies can retain molecular gases atmospheres which, upon cooling, have basal pressures of tens of bars or more. Pressure-induced opacity of these gases prevents such a body from eliminating its internal radioactive heat and its surface temperature can exceed for a long term the melting temperature of a life-supporting solvent. In this paper two non-aqueous but still polar solvents are considered: hydrogen sulfide and ammonia. Thermodynamic requirements to be fulfilled by a hypothetic gas constituent of a life-supporting FFP's atmosphere are studied. The three gases analyzed here (nitrogen, methane and ethane) are candidates. We show that bodies with ammonia oceans are possible in interstellar space. This may happen on FFPs of (significantly) smaller or larger mass than the Earth. Generally, in case of FFP smaller in size than the Earth, the atmosphere exhibits a convective layer near the surface and a radiative layer at higher altitudes while the atmosphere of FFPs larger in size than Earth does not exhibit a convective layer. The atmosphere mass of a life-hosting FFP of Earth size is two or three orders of magnitude larger than the mass of Earth atmosphere. For FFPs larger than the Earth and specific values of surface pressure and temperature, there are conditions for condensation (in the ethane atmosphere). Some arguments induce the conclusion than the associated surface pressures and temperatures should be treated with caution as appropriate life conditions.
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Liaw, Horng-Jang; Wang, Tzu-Ai
2007-03-06
Flash point is one of the major quantities used to characterize the fire and explosion hazard of liquids. Herein, a liquid with dissolved salt is presented in a salt-distillation process for separating close-boiling or azeotropic systems. The addition of salts to a liquid may reduce fire and explosion hazard. In this study, we have modified a previously proposed model for predicting the flash point of miscible mixtures to extend its application to solvent/salt mixtures. This modified model was verified by comparison with the experimental data for organic solvent/salt and aqueous-organic solvent/salt mixtures to confirm its efficacy in terms of prediction of the flash points of these mixtures. The experimental results confirm marked increases in liquid flash point increment with addition of inorganic salts relative to supplementation with equivalent quantities of water. Based on this evidence, it appears reasonable to suggest potential application for the model in assessment of the fire and explosion hazard for solvent/salt mixtures and, further, that addition of inorganic salts may prove useful for hazard reduction in flammable liquids.
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METHOD FOR SEPARATION OF PLUTONIUM FROM URANIUM AND FISSION PRODUCTS BY SOLVENT EXTRACTION
Seaborg, G.T.; Blaedel, W.J.; Walling, M.T. Jr.
1960-08-23
A process is given for separating from each other uranium, plutonium, and fission products in an aqueous nitric acid solution by the so-called Redox process. The plutonium is first oxidized to the hexavalent state, e.g., with a water-soluble dichromate or sodium bismuthate, preferably together with a holding oxidant such as potassium bromate. potassium permanganate, or an excess of the oxidizing agent. The solution is then contacted with a water-immiscible organic solvent, preferably hexone. whereby uranium and plutonium are extracted while the fission products remain in the aqueous solution. The separated organic phase is then contacted with an aqueous solution of a reducing agent, with or without a holding reductant (e.g., with a ferrous salt plus hydrazine or with ferrous sulfamate), whereby plutonium is reduced to the trivalent state and back- extracted into the aqueous solution. The uranium may finally be back-extracted from the organic solvent (e.g., with a 0.1 N nitric acid).
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Direct Assembly of Modified Proteins on Carbon Nanotubes in an Aqueous Solution
NASA Technical Reports Server (NTRS)
Kim, Jae-Woo; Lillehei, Peter T.; Park, Cheol; Harrison, Joycelyn S.
2007-01-01
Carbon nanotubes (CNTs) have superior mechanical and electrical properties that have opened up many potential applications. However, poor dispersibility and solubility, due to the substantial van der Waals attraction between tubes, have prevented the use of CNTs in practical applications, especially biotechnology applications. Effective dispersion of CNTs into small bundles or individual tubes in solvents is crucial to ensure homogeneous properties and enable practical applications. In addition to dispersion of CNTs into a solvent, the selection of appropriate solvent, which is compatible with a desired matrix, is an important factor to improve the mechanical, thermal, optical, and electrical properties of CNT-based fibers and composites. In particular, dispersion of CNTs into an aqueous system has been a challenge due to the hydrophobic nature of CNTs. Here we show an effective method for dispersion of both single wall CNTs (SWCNTs) and few wall CNTs (FWCNTs) in an aqueous buffer solution. We also show an assembly of cationized Pt-cored ferritins on the well dispersed CNTs in an aqueous buffer solution.
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Cloud condensation nuclei activation of limited solubility organic aerosol
NASA Astrophysics Data System (ADS)
Huff Hartz, Kara E.; Tischuk, Joshua E.; Chan, Man Nin; Chan, Chak K.; Donahue, Neil M.; Pandis, Spyros N.
The cloud condensation nuclei (CCN) activation of 19 organic species with water solubilities ( Csat) ranging from 10 -4 to 10 2 g solute 100 g -1 H 2O was measured. The organic particles were generated by nebulization of an aqueous or an alcohol solution. Use of alcohols as solvents enables the measurement of low solubility, non-volatile organic CCN activity and reduces the likelihood of residual water in the aerosol. The activation diameter of organic species with very low solubility in water ( Csat<0.3 g 100 g -1 H 2O) is in agreement with Köhler theory using the bulk solubility (limited solubility case) of the organic in water. Many species, including 2-acetylbenzoic acid, aspartic acid, azelaic acid, glutamic acid, homophthalic acid, phthalic acid, cis-pinonic acid, and salicylic acid are highly CCN active in spite of their low solubility (0.3 g 100 g -1 H 2O< Csat<1 g 100 g -1 H 2O), and activate almost as if completely water soluble. The CCN activity of most species is reduced, if the particles are produced using non-aqueous solvents. The existence of the particles in a metastable state at low RH can explain the observed enhancement in CCN activity beyond the levels suggested by their solubility.
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DMSO/base hydrolysis method for the disposal of high explosives and related energetic materials
Desmare, Gabriel W.; Cates, Dillard M.
2002-05-14
High explosives and related energetic materials are treated via a DMSO/base hydrolysis method which renders them non-explosive and/or non-energetic. For example, high explosives such as 1,3,5,7-tetraaza-1,3,5,7-tetranitrocyclooctane (HMX), 1,3,5-triaza-1,3,5-trinitrocyclohexane (RDX), 2,4,6-trinitrotoluene (TNT), or mixtures thereof, may be dissolved in a polar, aprotic solvent and subsequently hydrolyzed by adding the explosive-containing solution to concentrated aqueous base. Major hydrolysis products typically include nitrite, formate, and nitrous oxide.
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Analytical applications of emulsions and microemulsions.
Burguera, José Luis; Burguera, Marcela
2012-07-15
Dispersion systems like emulsions and microemulsions are able to solubilize both polar and non-polar substances due to the special arrangement of the oil and aqueous phases. The main advantages of using emulsions or microemulsions in analytical chemistry are that they do not require the previous destruction of the sample matrix or the use of organic solvents as diluents, and behave similarly to aqueous solutions, frequently allowing the use of aqueous standard solutions for calibration. However, it appears that there are many contradictory concepts and misunderstandings often related to terms definition when referring to such systems. The main aim of this review is to outline the differences between these two aggregates and to give an overview of the most recent advances on their analytical applications with emphasis on the potentiality of the on-line emulsification processes. Copyright © 2012 Elsevier B.V. All rights reserved.
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Chang, Lin; Shao, Qian; Xi, Xingjun; Chu, Qiao; Wei, Yun
2017-02-01
Aqueous two-phase flotation followed by preparative high-performance liquid chromatography was used to separate four flavonol glycosides from Solanum rostratum Dunal. In the aqueous two-phase flotation section, the effects of sublation solvent, solution pH, (NH 4 ) 2 SO 4 concentration in aqueous solution, cosolvent, N 2 flow rate, flotation time, and volumes of the polyethylene glycol phase on the recovery were investigated in detail, and the optimal conditions were selected: 50 wt% polyethylene glycol 1000 ethanol solvent as the flotation solvent, pH 4, 350 g/L of (NH 4 ) 2 SO 4 concentration in aqueous phase, 40 mL/min of N 2 flow rate, 30 min of flotation time, 10.0 mL of flotation solvent volume, and two times. After aqueous two-phase flotation concentration, the flotation products were purified by preparative high-performance liquid chromatography. The purities of the final products A and B were 98.1 and 99.0%. Product B was the mixture of three compounds based on the analysis of high-performance liquid chromatography at the temperature of 10°C, while product A was hyperoside after the identification by nuclear magnetic resonance. Astragalin, 3'-O-methylquercetin 3-O-β-d-galactopyranoside, and 3'-O-methylquercetin 3-O-β-d-glucopyranoside were obtained with the purity of 93.8, 97.1, and 99.2%, respectively, after the further separation of product B using preparative high-performance liquid chromatography. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Bruce, F.R.
1962-07-24
A solvent extraction process was developed for separating actinide elements including plutonium and uranium from fission products. By this method the ion content of the acidic aqueous solution is adjusted so that it contains more equivalents of total metal ions than equivalents of nitrate ions. Under these conditions the extractability of fission products is greatly decreased. (AEC)
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Force Induced Globule-to-Coil Transition of Single Polymer Chains.
NASA Astrophysics Data System (ADS)
Gunari, Nikhil; Walker, Gilbert
2008-03-01
Force induced structural transitions of individual homopolymer chains have been studied in different solvent conditions using single molecule force spectroscopy. Single molecule mechanics in the ``fly-fishing'' mode showed a first-order like transition for polystyrene (PS) in water exhibiting a characteristic three regime force extension curve. In contrast, poly methylmethacrylate (PMMA) showed a characteristic saw-tooth pattern reminiscent of multidomain disassembly behavior similar to that seen in modular protein mechanics. The plateau force for PS and the saw-tooth pattern for PMMA disappear when measured in aqueous guanidine hydrochloride solution and in other non-solvents showing that the characteristic deformational behavior observed for the two polymers in water may be due to hydrophobic interactions .
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Ai, Guomin; Sun, Tong; Dong, Xiuzhu
2014-08-15
Methanol, ethanol, and acetic acid are not easily extracted from aqueous samples and are susceptible to isotope fractionation in gas chromatography/isotope ratio mass spectrometry (GC/IRMS) analysis. Developing a direct dilution GC/IRMS method for aqueous samples, by adjusting the sample concentrations in common solvents to be similar to each other and using a fixed GC split ratio, is very convenient and important because any linearity effects caused by amount-dependent isotope fractionation can be avoided. The suitability of acetonitrile and acetone solvents for the GC/IRMS analysis of pure methanol, ethanol and acetic acid, and commercial liquor and vinegar samples was evaluated using n-hexane and water as control solvents. All the solvents including water were separated from the analyte on a HP-INNOWAX column and were diverted away from the combustion interface. The influence of liquor matrix on the ethanol GC/IRMS analyses was evaluated by adding pure ethanol to liquor samples. Acetonitrile and acetone gave similar δ(13) C values for pure ethanol and pure acetic acid to those obtained in water and n-hexane, and also gave similar δ(13) C values of ethanol in liquor and acetic acid in white vinegar to that obtained in water. For methanol analysis, acetonitrile and refined acetone gave similar δ(13) C values to that obtained in water, but n-hexane was not a suitable solvent. In addition, isotopic fractionation caused by solvent and solute interactions was observed. We recommend using acetonitrile for the GC/IRMS analysis of aqueous alcoholic samples, and acetone for the analysis of aqueous acetic acid samples. This direct dilution method can provide high accurate and precise GC/IRMS analysis of the relative changes in δ(13) C values of methanol, ethanol, and acetic acid. Copyright © 2014 John Wiley & Sons, Ltd.
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Pandey, Ashish; Pandey, Siddharth
2014-12-18
Deep eutectic solvents (DESs) have shown potential as promising environmentally friendly alternatives to conventional solvents. Many common and popular DESs are obtained by simply mixing a salt and a H-bond donor. Properties of such a DES depend on its constituents. Change in temperature and addition of water, a benign cosolvent, can change the physicochemical properties of DESs. The effect of changing temperature and addition of water on solvatochromic probe behavior within three DESs formed from choline chloride combined with 1,2-ethanediol, glycerol, and urea, respectively, in 1:2 mol ratios termed ethaline, glyceline, and reline is presented. Increase in temperature results in reduced H-bond donating acidity of the DESs. Dipolarity/polarizability and H-bond accepting basicity do not change with changing temperature of the DESs. The response of the fluorescence probe pyrene also indicates a decrease in the polarity of the DESs as temperature is increased. Addition of water to DES results in increased dipolarity/polarizability and a decrease in H-bond accepting basicity. Except for pyrene, solvatochromic probes exhibit responses close to those predicted from ideal-additive behavior with slight preferential solvation by DES within the aqueous mixtures. Pyrene response reveals significant preferential solvation by DES and/or the presence of solvent-solvent interactions, especially within aqueous mixtures of ethaline and glyceline, the DESs constituted of H-bond donors with hydroxyl functionalities. FTIR absorbance and Raman spectroscopic measurements of aqueous DES mixtures support the outcomes from solvatochromic probe responses. Aqueous mixtures of ethaline and glyceline possess relatively more interspecies H-bonds as compared to aqueous mixtures of reline, where interstitial accommodation of water within the reline molecular network appears to dominate.
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SEPARATION PROCESS FOR ZIRCONIUM AND COMPOUNDS THEREOF
Crandall, H.W.; Thomas, J.R.
1959-06-30
The separation of zirconium from columbium, rare earths, yttrium and the alkaline earth metals, such mixtures of elements occurring in zirconium ores or neutron irradiated uranium is described. According to the invention a suitable separation of zirconium from a one normal acidic aqueous solution containing salts, nitrates for example, of tetravalent zirconium, pentavalent columbium, yttrium, rare earths in the trivalent state and alkaline earths can be obtained by contacting the aqueous solution with a fluorinated beta diketonc alone or in an organic solvent solution, such as benzene, to form a zirconium chelate compound. When the organic solvent is present the zirconium chelate compound is directly extracted; otherwise it is separated by filtration. The zirconium may be recovered from contacting the organic solvent solution containing the chelated compound by back extraction with either an aqueous hydrofluoric acid or an oxalic acid solution.
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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.
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Mechanism of protein precipitation and stabilization by co-solvents
NASA Astrophysics Data System (ADS)
Timasheff, Serge N.; Arakawa, Tsutomu
1988-07-01
The interactions between proteins and a number of substances which, when present at high concentration, stabilize or precipitate proteins, have been analyzed in terms of the preferential interactions of these co-solvents with proteins. In all cases, stabilization or precipitation was accompanied by preferential exclusion of the co-solvent from the immediate domain of the protein, i.e., preferential hydration of the protein. This means that addition of the co-solvent to the aqueous protein solution increased the chemical potentials of both components. The thermodynamic interaction parameters derived from such data make it possible to calculate the salting out constant, Ks, as well as to construct a phase isotherm for any given solvent mixture which indicates the limiting protein solubility. The salting-out effect can be decomposed into contributions from non-specific preferential exclusion and specific binding of the ligand to the protein, the balance leading to solubilization or precipitation. In reactions, such as denaturation, the effect of co-solvent on the reaction depends on the difference in the preferential interactions of the two end states of the protein. Principal sources of preferential exclusion have been identified as steric exclusion, increase of the surface tension of water by the co-solvent, repulsion by charged loci on the protein and solvophobicity.
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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
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Investigation of the pharmaceutical and pharmacological equivalence of different Hawthorn extracts.
Vierling, W; Brand, N; Gaedcke, F; Sensch, K H; Schneider, E; Scholz, M
2003-01-01
Seven Hawthorn extracts were tested in isolated guinea pig aorta rings. The effect on noradrenaline- (10 microM) induced contraction was investigated. The extracts were prepared using ethanol (40 to 70% v/v), methanol (40 to 70% v/v), and water as the extraction solvents. The aqueous-alcoholic extracts displayed similar spectra of constituents. They were characterised by similar procyanidin, flavonoid, total vitexin and total phenols content and by similar TLC fingerprint chromatograms. The aqueous extract, however, showed a different fingerprint and a noticeably lower concentration of procyanidins, flavonoids and total phenols but a similar total vitexin content. All 7 extracts had a relaxant effect on the aorta precontracted by noradrenaline and led to relaxations to 44 until 29% of the initial values. The EC50 values of the aqueous-alcoholic extracts varied between 4.16 and 9.8 mg/l. The aqueous extract produced a similarly strong maximal relaxation as the other extracts, but the EC50, at 22.39 mg/l, was markedly higher. The results show that Hawthorn extracts with comparable quality profiles were obtained by using aqueous-alcoholic extraction solvents (40 to 70% ethanol or methanol). The extracts exerted comparable pharmacological effects. When using water as the extraction solvent, both, the spectrum of constituents and the pharmacological effect, deviated remarkably. It is thus possible to obtain bioequivalent extracts with comparable effect profiles by using 40 to 70% ethanol or methanol as the extraction solvent.
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Comparison of starch and gelatin hydrogels for non-toxic supercapacitor electrolytes
NASA Astrophysics Data System (ADS)
Railanmaa, Anna; Lehtimäki, Suvi; Lupo, Donald
2017-06-01
Starch and gelatin are two of the most abundantly available natural polymers. Their non-toxicity, low cost, and compatibility with aqueous solvents make them ideal for use in ubiquitous, environmentally friendly electronics systems. This work presents the results of conductivity measurements through impedance spectroscopy for gelatin- and starch-based aqueous gel electrolytes. The NaCl-based gels were physically cross-linked. The conductivity values were 84.6 mS/cm at 1.5 mol L-1 and 71.5 mS/cm at 2 mol L-1 for gelatin and starch, respectively. The mechanical properties of gelatin were found preferable to those of starch, although they deteriorated significantly when the salt concentration exceeded 2 mol L-1. The ability of the gels to successfully act as a supercapacitor electrolyte was demonstrated with printed electrodes on plastic substrate. The devices were characterized through cyclic voltammetry measurements. The results imply that these polymer gel electrolytes are very promising for replacing the traditional aqueous liquid electrolytes in supercapacitors in applications where, for example, user and environmental safety is essential.
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A Non-catalytic Deep Desulphurization Process using Hydrodynamic Cavitation
Suryawanshi, Nalinee B.; Bhandari, Vinay M.; Sorokhaibam, Laxmi Gayatri; Ranade, Vivek V.
2016-01-01
A novel approach is developed for desulphurization of fuels or organics without use of catalyst. In this process, organic and aqueous phases are mixed in a predefined manner under ambient conditions and passed through a cavitating device. Vapor cavities formed in the cavitating device are then collapsed which generate (in-situ) oxidizing species which react with the sulphur moiety resulting in the removal of sulphur from the organic phase. In this work, vortex diode was used as a cavitating device. Three organic solvents (n-octane, toluene and n-octanol) containing known amount of a model sulphur compound (thiophene) up to initial concentrations of 500 ppm were used to verify the proposed method. A very high removal of sulphur content to the extent of 100% was demonstrated. The nature of organic phase and the ratio of aqueous to organic phase were found to be the most important process parameters. The results were also verified and substantiated using commercial diesel as a solvent. The developed process has great potential for deep of various organics, in general, and for transportation fuels, in particular. PMID:27605492
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A Non-catalytic Deep Desulphurization Process using Hydrodynamic Cavitation.
Suryawanshi, Nalinee B; Bhandari, Vinay M; Sorokhaibam, Laxmi Gayatri; Ranade, Vivek V
2016-09-08
A novel approach is developed for desulphurization of fuels or organics without use of catalyst. In this process, organic and aqueous phases are mixed in a predefined manner under ambient conditions and passed through a cavitating device. Vapor cavities formed in the cavitating device are then collapsed which generate (in-situ) oxidizing species which react with the sulphur moiety resulting in the removal of sulphur from the organic phase. In this work, vortex diode was used as a cavitating device. Three organic solvents (n-octane, toluene and n-octanol) containing known amount of a model sulphur compound (thiophene) up to initial concentrations of 500 ppm were used to verify the proposed method. A very high removal of sulphur content to the extent of 100% was demonstrated. The nature of organic phase and the ratio of aqueous to organic phase were found to be the most important process parameters. The results were also verified and substantiated using commercial diesel as a solvent. The developed process has great potential for deep of various organics, in general, and for transportation fuels, in particular.
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A Non-catalytic Deep Desulphurization Process using Hydrodynamic Cavitation
NASA Astrophysics Data System (ADS)
Suryawanshi, Nalinee B.; Bhandari, Vinay M.; Sorokhaibam, Laxmi Gayatri; Ranade, Vivek V.
2016-09-01
A novel approach is developed for desulphurization of fuels or organics without use of catalyst. In this process, organic and aqueous phases are mixed in a predefined manner under ambient conditions and passed through a cavitating device. Vapor cavities formed in the cavitating device are then collapsed which generate (in-situ) oxidizing species which react with the sulphur moiety resulting in the removal of sulphur from the organic phase. In this work, vortex diode was used as a cavitating device. Three organic solvents (n-octane, toluene and n-octanol) containing known amount of a model sulphur compound (thiophene) up to initial concentrations of 500 ppm were used to verify the proposed method. A very high removal of sulphur content to the extent of 100% was demonstrated. The nature of organic phase and the ratio of aqueous to organic phase were found to be the most important process parameters. The results were also verified and substantiated using commercial diesel as a solvent. The developed process has great potential for deep of various organics, in general, and for transportation fuels, in particular.
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Mazzini, Virginia
2017-01-01
The importance of electrolyte solutions cannot be overstated. Beyond the ionic strength of electrolyte solutions the specific nature of the ions present is vital in controlling a host of properties. Therefore ion specificity is fundamentally important in physical chemistry, engineering and biology. The observation that the strengths of the effect of ions often follows well established series suggests that a single predictive and quantitative description of specific-ion effects covering a wide range of systems is possible. Such a theory would revolutionise applications of physical chemistry from polymer precipitation to drug design. Current approaches to understanding specific-ion effects involve consideration of the ions themselves, the solvent and relevant interfaces and the interactions between them. Here we investigate the specific-ion effects trends of standard partial molar volumes and electrostrictive volumes of electrolytes in water and eleven non-aqueous solvents. We choose these measures as they relate to bulk properties at infinite dilution, therefore they are the simplest electrolyte systems. This is done to test the hypothesis that the ions alone exhibit a specific-ion effect series that is independent of the solvent and unrelated to surface properties. The specific-ion effects trends of standard partial molar volumes and normalised electrostrictive volumes examined in this work show a fundamental ion-specific series that is reproduced across the solvents, which is the Hofmeister series for anions and the reverse lyotropic series for cations, supporting the hypothesis. This outcome is important in demonstrating that ion specificity is observed at infinite dilution and demonstrates that the complexity observed in the manifestation of specific-ion effects in a very wide range of systems is due to perturbations of solvent, surfaces and concentration on the underlying fundamental series. This knowledge will guide a general understanding of specific-ion effects and assist in the development of a quantitative predictive theory of ion specificity. PMID:29147533
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Zhang, Shao Fei; Chen, Peng Hao; Zhang, Fei; Yang, Yan Fang; Liu, De Kun; Wu, Gang
2013-12-18
Emamectin benzoate is highly effective against insect pests and widely used in the world. However, its biological activity is limited because of high resistance of target insects and rapid degradation speed in fields. Preparation and physicochemical characterization of degradable microcapsules of emamectin benzoate were studied by modified solvent evaporation/extraction method using polylactide (PLA) as wall material. The influence of different compositions of the solvent in internal organic phase and external aqueous phase on diameter, span, pesticide loading, and entrapment rate of the microspheres was investigated. The results indicated that the process of solvent extraction and the formation of the microcapsules would be accelerated by adding water-miscible organic solvents such as ethyl ether, acetone, ethyl acetate, or n-butanol into internal organic phase and external aqueous phase. Accelerated formation of the microcapsules would result in entrapment rates of emamectin benzoate increased to as high as 97%. In addition, by adding ethanol into the external aqueous phase, diameters would reduce to 6.28 μm, whereas the loading efficiency of emamectin benzoate did not increase. The PLA microspheres prepared under optimum conditions were smoother and more spherical. The degradation rate in PLA microspheres of emamectin benzoate on the 10th day was 4.29 ± 0.74%, whereas the degradation rates of emamectin benzoate in methanol solution and solid technical material were 46.3 ± 2.11 and 22.7 ± 1.51%, respectively. The PLA skeleton had combined with emamectin benzoate in an amorphous or molecular state by using differential scanning calorimetry (DSC) determination. The results indicated that PLA microspheres of emamectin benzoate with high entrapment rate, loading efficiency, and physicochemical characteristics could be obtained by adding water-miscible organic solvents into the internal organic phase and external aqueous phase.
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Enzyme and Chemical Encapsulation in Polymeric Microcapsules,
1995-01-01
Polypyrrole microcapsules (prepared via the template method) were used for immobilization of both enzymatic and chemical catalytic systems. Enzymes...immobilized Pd nanoparticles for catalysis of hydrogen peroxide decomposition. Microcapsules loaded with glucose oxidase (GOD) were found to have...from the capsules; no leakage was observed. Subtilisin was used to show that these microcapsules can be used in non-aqueous solvents. The effect of capsule wall thickness on the rate of enzymatic reaction was also explored.
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NASA Astrophysics Data System (ADS)
Shirayama, Sakae; Uda, Tetsuya
2016-04-01
This research outlines an organic-aqueous-aqueous three-phase solvent extraction method and proposes its use in a new metal separation process for the recycling of manganese (Mn), cobalt (Co), and nickel (Ni) from used lithium ion batteries (LIBs). The three-phase system was formed by mixing xylene organic solution, 50 pct polyethylene glycol (PEG) aqueous solution, and 1 mol L-1 sodium sulfate (Na2SO4) aqueous solution. The xylene organic solution contained 2-ethylhexylphosphonic acid (D2EHPA) as an extractant for Mn ion, and the Na2SO4 aqueous solution contained 1 mol L-1 potassium thiocyanate (KSCN) as an extractant for Co ion. Concentrations of the metal ions were varied by dissolving metal sulfates in the Na2SO4 aqueous solution. As a result of the experiments, Mn, Co, and Ni ions were distributed in the xylene organic phase, PEG-rich aqueous phase, and Na2SO4-rich aqueous phase, respectively. The separation was effective when the pH value was around 4. Numerical simulation was also conducted in order to predict the distribution of metal ions after the multi-stage counter-current extractions.
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Bandforuzi, Samereh Ranjbar; Hadjmohammadi, Mohammad Reza
2018-08-03
The extraction of phthalate esters (PEs) from aqueous matrices using two-phase solvent bar microextraction by organic micellar phase was investigated. A short hollow fiber immobilized with reverse micelles of Brij 35 surfactant in 1-octanol was served as the solvent bar for microextraction. Experimental results show that the extraction efficiency were much higher using two-phase solvent bar microextraction based on non-ionic surfactant than conventional two-phase solvent bar microextraction because of a positive effect of surfactant-containing extraction phase in promoting the partition process by non-ionic intermolecular forces such as polar and hydrophobicity interactions. The nature of the extraction solvent, type and concentration of non-ionic surfactant, extraction time, sample pH, temperature, stirring rate and ionic strength were the effecting parameters which optimized to obtain the highest extraction recovery. Analysis of recovered analytes was carried out with high performance liquid chromatography coupled with ultraviolet detection (HPLC-UV). Under the optimum conditions, linearity was observed in the range of 1-800 ng mL -1 for dimethylphthalate (DMP) and 0.5-800 ng mL -1 for diethylphthalate (DEP) and di-n-butyl phthalate (DBP) with correlation determination values above 0.99 for them. The limits of detection and quantification were ranged from 0.012 to 0.03 ng mL -1 and 0.04-0.1 ng mL -1 , respectively. The ranges of intra-day and inter-day RSD (n = 3) at 20 ng mL -1 of PEs were 1.8-2.1% and 2.1-2.6%, respectively. Results showed that developed method can be a very powerful, innovative and promising sample preparation technique in PEs analysis from environmental and drinking water samples. Copyright © 2018. Published by Elsevier B.V.
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NASA Astrophysics Data System (ADS)
Li, Yun; Sniekers, Jeroen; Malaquias, João C.; Van Goethem, Cedric; Binnemans, Koen; Fransaer, Jan; Vankelecom, Ivo F. J.
2018-02-01
A stable and eco-friendly anion-exchange membrane (AEM) was prepared and applied in a non-aqueous all-copper redox flow battery (RFB). The AEM was prepared via a simple procedure, leading to a cross-linked structure containing quaternary ammonium groups without involvement of harmful trimethylamine. A network was thus constructed which ensured both ion transport and solvent resistance. The ion exchange capacity (IEC) of the membrane was tuned from 0.49 to 1.03 meq g-1 by varying the content of the 4, 4‧-bipyridine crosslinking agent. The membrane showed a good anion conductivity and retention of copper ions. As a proof of principle, a RFB single cell with this crosslinked membrane yielded a coulombic efficiency of 89%, a voltage efficiency of 61% and an energy efficiency of 54% at 7.5 mA cm-2.
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Clegg, Helen; Riding, Matthew J; Oliver, Robin; Jones, Kevin C; Semple, Kirk T
2014-08-15
As soils represent a major sink for most pesticides, factors influencing pesticide degradation are essential in identifying their potential environmental risk. Desorption of (14)C-azoxystrobin was investigated over time in two soils under sterile and non-sterile conditions using exhaustive (solvent) and non-exhaustive (aqueous) methods. Desorption data were fitted to a two-compartment model, differentiating between fast and slow desorbing fractions. With increased ageing, rapid desorption (Frap) (bioaccessibility) decreased with corresponding increases in slowly desorbing fractions (F(slow)). The rapid desorption rate constant (k(fast)) was not affected by ageing, sterility or extraction solvent. The non-exhaustive extractions had similar desorption profiles; whereas exhaustive extractions in aged soils had the highest F(rap). In non-sterile soil, F(rap) was lower resulting in higher F(slow), while desorption rates remained unaffected. Organic matter (OM) reduces F(rap); but not desorption rates. Microorganisms and OM enhanced ageing effects, reducing the fraction of fast desorbing chemicals and potentially the bioaccessibility of pesticides in soil. Copyright © 2014 Elsevier B.V. All rights reserved.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Law, J.D.; Brewer, K.N.; Herbst, R.S.
1996-09-01
TRUEX is being evaluated at Idaho Chemical Processing Plant (ICPP) for separating actinides from acidic radioactive waste stored at ICPP; efforts have culminated in a recent demonstration with actual tank waste. A continuous countercurrent flowsheet test was successfully completed at ICPP using waste from tank WM-183. This demonstration was performed using 24 states of 2-cm dia centrifugal contactors in the shielded hot cell at the ICPP Remote Analytical Laboratory. The flowsheet had 8 extraction stages, 5 scrub stages, 6 strip stages, 3 solvent wash stages, and 2 acid rinse stages. A centrifugal contactor stage in the scrub section was notmore » working during testing, and the scrub feed (aqueous) solution followed the solvent into the strip section, eliminating the scrub section in the flowsheet. An overall removal efficiency of 99.97% was obtained for the actinides, reducing the activity from 457 nCi/g in the feed to 0.12 nCi/g in the aqueous raffinate, well below the NRC Class A LLW requirement of 10 nCi/g for non-TRU waste.The 0.04 M HEDPA strip section back-extracted 99.9998% of the actinide from the TRUEX solvent. Removal efficiencies of >99. 90, 99.96, 99.98, >98.89, 93.3, and 89% were obtained for {sup 241}Am, {sup 238}Pu, {sup 239}Pu, {sup 235}U, {sup 238}U, and {sup 99}Tc. Fe was partially extracted by the TRUEX solvent, resulting in 23% of the Fe exiting in the strip product. Hg was also extracted by the TRUEX solvent (73%) and stripped from the solvent in the 0.25 M Na2CO3 wash section. Only 1.4% of the Hg exited with the high activity waste strip product.« less
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Simple, benign, aqueous-based amination of polycarbonate surfaces
VanDelinder, Virginia; Wheeler, David R.; Small, Leo J.; ...
2015-03-18
Here we report a simple, safe, environmentally-friendly aqueous method that uses diamines to functionalize a polycarbonate surface with amino groups. We demonstrate the ability of this facile method to serve as a foundation upon which other functionalities may be attached, including anti-fouling coatings and oriented membrane proteins. The use of water as the solvent for the functionalization ensures that solvent induced swelling does not affect the optical or mechanical properties of the polycarbonate.
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Nforneh, Benjamen; Warncke, Kurt
2017-12-14
Electron paramagnetic resonance spectroscopy of the spin probe, TEMPOL, is used to resolve solvent phases that surround the ethanolamine ammonia-lyase (EAL) protein from Salmonella typhimurium at low temperature (T) in frozen, globally polycrystalline aqueous solution and to report on the T dependence of their detectably rigid and fluid states. EAL plays a role in human gut microbiome-based disease conditions, and physicochemical studies provide insight into protein structure and mechanism, toward potential therapeutics. Temperature dependences of the rotational correlation times (τ c ; detection range, 10 -11 ≤ τ c ≤ 10 -7 s) and the corresponding weights of TEMPOL tumbling components from 200 to 265 K in the presence of EAL are measured in two frozen systems: (1) water-only and (2) 1% v/v dimethyl sulfoxide (DMSO). In the water-only condition, a protein-vicinal solvent component detectably fluidizes at 230 K and melts the surrounding ice-crystalline region with increasing T, creating a bounded, relatively high-viscosity aqueous solvent domain, up to 265 K. In the EAL, 1% v/v DMSO condition, two distinct concentric solvent phases are resolved around EAL: protein-associated domain (PAD) and mesodomain. The DMSO aqueous mesodomain fluidizes at 200 K, followed by PAD fluidization at 210 K. The interphase dynamical coupling is consistent with the spatial arrangement and significant contact areas of the phases, indicated by the experimentally determined mean volume ratio, V(mesodomain)/V(PAD)/V(protein) = 0.5:0.3:1.0. The results provide a rationale for native chemical reactions of EAL at T < 250 K and an advance toward precise control of solvent dynamics as a tunable parameter for quantifying the coupling between solvent and protein fluctuations and chemical reaction steps in EAL and other enzymes.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Beste, Ariana; Attalla, Moetaz; Jackson, Phil
2012-01-01
A meta GGA-DFT study of CO{sub 2} activation in aqueous ammonia solutions, with an emphasis on the reaction barrier and molecularity, has been undertaken using the M06-2X functional with an augmented triple-zeta split-valence basis set (6-311++G(d,p)). Up to five base molecules were treated explicitly in order to establish the effects of solvent catalysis in the chemical capture process. Aqueous free energies of solvation were determined for optimized reactant and transition structures using SM8/M06-2X/6-311++G(d,p). The concept of the solvent pre-complex as presented by Dixon and coworkers (Nguyen, M. T.; Matus, M. H.; Jackson, V. E.; Ngan, V. T.; Rustad, J. R.;more » Dixon, D. A. J. Phys. Chem. A 2008, 112, 10386-10398) was exploited to account for the energetics of disruption of the hydrogen-bonding solvent nano-network prior to the CO{sub 2} activation step. Selected gas- and aqueous-phase thermodynamic quantities have also been derived.« less
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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.
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NASA Astrophysics Data System (ADS)
Deosarkar, S. D.; Puyad, A. L.; Shaikh, U. B.; Solanke, S. S.
2014-04-01
Densities, viscosities, and refractive indices of aqueous solutions of hydroxylamine hydrochloride containing 0.05, 0.10, and 0.15 mol/dm3 NaCl, KCl, and NH4Cl were measured at different concentrations of hydroxylamine hydrochloride at 30°C. Viscosity coefficients A and B representing ion-ion and ion-solvent interactions were determined from Jones-Dole equation. Experimental properties and viscosity coefficients have been interpreted in terms of ion-ion and ion-solvent interactions. Ion-solvent interactions were found to be dominating over the ion-ion interactions in studied systems.
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Modelling the aqueous and nonaqueous interfaces for CO2 electro-reduction over Sn catalysts
NASA Astrophysics Data System (ADS)
Sheng, Tian; Sun, Shi-Gang
2018-01-01
In CO2 electroreduction, Sn catalysts with a high overpotential for hydrogen evolution reaction and a high selectivity towards formic acid formation are very attractive. Many efforts have been made for improving the catalytic performance and for understanding the mechanisms. In electrochemistry, the role of solvents for surface reactions was deserved to be investigated, in particular for some nonaqueous solvents. Here, we have modeled the aqueous (water) and nonaqueous (acetonitrile and dichloromethane) for investigation of CO2 electroreduction on Sn surface, by constrained ab initio molecular dynamics simulations and thermodynamic integrations, including a number of explicit solvent molecules in computational models. It was found that CO2 reduction is initiated from formate formation and solvents, in particular, water can effectively facilitate the reaction.
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Wan Ibrahim, Wan Nazihah; Sanagi, Mohd Marsin; Mohamad Hanapi, Nor Suhaila; Kamaruzaman, Sazlinda; Yahaya, Noorfatimah; Wan Ibrahim, Wan Aini
2018-06-07
We describe the preparation, characterization and application of a composite film adsorbent based on blended agarose-chitosan-multi-walled carbon nanotubes for the preconcentration of selected non-steroidal anti-inflammatory drugs in aqueous samples before determination by high-performance liquid chromatography with UV detection. The composite film showed high surface area (4.0258 m 2 /g) and strong hydrogen bonding between multi-walled carbon nanotubes and agarose/chitosan matrix, which prevent adsorbent deactivation and ensure long-term stability. Several parameters, namely, sample pH, addition of salt, extraction time, desorption solvent and concentration of multi-walled carbon nanotubes in the composite film were optimized using a one-factor-at-time approach. The optimum extraction conditions obtained were as follows: isopropanol as conditioning solvent, 10 mL of sample solution at pH 2, extraction time of 30 min, stirring speed of 600 rpm, 100 μL of isopropanol as desorption solvent, desorption time of 5 min under ultrasonication, and 0.4% w/v of composite film. Under optimized conditions, the calibration curved showed good linearity in the range of 1-500 ng/mL (r 2 = 0.997-0.999), good limits of detection (0.89-8.05 ng/mL) were obtained with good relative standard deviations of < 4.59% (n = 3) for the determination of naproxen, diclofenac sodium salt and mefenamic acid drugs. This article is protected by copyright. All rights reserved. This article is protected by copyright. All rights reserved.
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Method for removing organic liquids from aqueous solutions and mixtures
Hrubesh, Lawrence W.; Coronado, Paul R.; Dow, Jerome P.
2004-03-23
A method for removing organic liquids from aqueous solutions and mixtures. The method employs any porous material preferably in granular form and having small pores and a large specific surface area, that is hydrophobic so that liquid water does not readily wet its surface. In this method, organics, especially organic solvents that mix with and are more volatile than water, are separated from aqueous solution by preferentially evaporating across the liquid/solid boundary formed at the surfaces of the hydrophobic porous materials. Also, organic solvents that are immiscible with water, preferentially wet the surfaces of the hydrophobic material and are drawn within the porous materials by capillary action.
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Chen, Yuehua; Wang, Huiyong; Wang, Jianji
2014-05-01
Thermodynamic dissociation constants of the Brønsted acidic ionic liquids (ILs) are important for their catalytic and separation applications. In this work, a series of imidazolium bromides with one carboxylic acid substitute group in their alkyl chain ([{(CH2)nCOOH}mim]Br, n = 1,3,5,7) have been synthesized, and their dissociation constants (pKa) at different ionic strengths have been determined in aqueous and aqueous organic solvents at 0.1 mole fraction (x) of ethanol, glycol, iso-propanol, and dimethyl sulfoxide by potentiometric titrations at 298.2 K. The standard thermodynamic dissociation constants (pKa(T)) of the ILs in these solvents were calculated from the extended Debye-Hückel equation. It was found that the pKa values increased with the increase of ionic strength of the media and of the addition of organic solvent in water. The pKa(T) values also increased with the increase of the alkyl chain length of cations of the ILs. In addition, the effect of solvent nature on pKa(T) values is interpreted from solvation of the dissociation components and their Gibbs energy of transfer from water to aqueous organic solutions.
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NASA Astrophysics Data System (ADS)
Lawrence, Adrian; Stuart, Marianne; Cheney, Colin; Jones, Neil; Moss, Richard
2006-12-01
Contaminant migration behaviour in the unsaturated zone of a fractured porous aquifer is discussed in the context of a study site in Cheshire, UK. The site is situated on gently dipping sandstones, adjacent to a linear lagoon historically used to dispose of industrial wastes containing chlorinated solvents. Two cores of more than 100 m length were recovered and measurements of chlorinated hydrocarbons (CHCs), inorganic chemistry, lithology, fracturing and aquifer properties were made. The results show that selecting an appropriate vertical sampling density is crucial both to providing an understanding of contaminant pathways and distinguishing whether CHCs are present in the aqueous or non-aqueous phase. The spacing of such sampling should be on a similar scale to the heterogeneity that controls water and contaminant movement. For some sections of the Permo-Triassic aquifer, significant changes in lithology and permeability occur over vertical distances of less than 1 m and samples need to be collected at this interval, otherwise considerable resolution is lost, potentially leading to erroneous interpretation of data. At this site, although CHC concentrations were high, the consistent ratio of the two main components of the plume (tetrachloroethene and trichloroethene) provided evidence of movement in the aqueous phase rather than in dense non-aqueous phase liquid (DNAPL).
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Structural stability of proteins in aqueous and nonpolar environments
NASA Astrophysics Data System (ADS)
Yasuda, Satoshi; Oshima, Hiraku; Kinoshita, Masahiro
2012-10-01
A protein folds into its native structure with the α-helix and/or β-sheet in aqueous solution under the physiological condition. The relative content of these secondary structures largely varies from protein to protein. However, such structural variability is not exhibited in nonaqueous environment. For example, there is a strong trend that alcohol induces a protein to form α-helices, and many of the membrane proteins within the lipid bilayer consists of α-helices. Here we investigate the structural stability of proteins in aqueous and nonpolar environments using our recently developed free-energy function F = (Λ - TS)/(kBT0) = Λ/(kBT0) - S/kB (T0 = 298 K and the absolute temperature T is set at T0) which is based on statistical thermodynamics. Λ/(kBT0) and S/kB are the energetic and entropic components, respectively, and kB is Boltzmann's constant. A smaller value of the positive quantity, -S, represents higher efficiency of the backbone and side-chain packing promoted by the entropic effect arising from the translational displacement of solvent molecules or the CH2, CH3, and CH groups which constitute nonpolar chains of lipid molecules. As for Λ, in aqueous solution, a transition to a more compact structure of a protein accompanies the break of protein-solvent hydrogen bonds: As the number of donors and acceptors buried without protein intramolecular hydrogen bonding increases, Λ becomes higher. In nonpolar solvent, lower Λ simply implies more intramolecular hydrogen bonds formed. We find the following. The α-helix and β-sheet are advantageous with respect to -S as well as Λ and to be formed as much as possible. In aqueous solution, the solvent-entropy effect on the structural stability is so strong that the close packing of side chains is dominantly important, and the α-helix and β-sheet contents are judiciously adjusted to accomplish it. In nonpolar solvent, the solvent-entropy effect is substantially weaker than in aqueous solution. Λ is crucial and the α-helix is more stable than the β-sheet in terms of Λ, which develops a tendency that α-helices are exclusively chosen. For a membrane protein, α-helices are stabilized as fundamental structural units for the same reason, but their arrangement is performed through the entropic effect mentioned above.
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The Search for Nonflammable Solvent Alternatives for Cleaning Aerospace Oxygen Systems
NASA Technical Reports Server (NTRS)
Mitchell, Mark; Lowrey, Nikki
2012-01-01
Oxygen systems are susceptible to fires caused by particle and nonvolatile residue (NVR) contaminants, therefore cleaning and verification is essential for system safety. . Cleaning solvents used on oxygen system components must be either nonflammable in pure oxygen or complete removal must be assured for system safety. . CFC -113 was the solvent of choice before 1996 because it was effective, least toxic, compatible with most materials of construction, and non ]reactive with oxygen. When CFC -113 was phased out in 1996, HCFC -225 was selected as an interim replacement for cleaning propulsion oxygen systems at NASA. HCFC-225 production phase-out date is 01/01/2015. HCFC ]225 (AK ]225G) is used extensively at Marshall Space Flight Center and Stennis Space Center for cleaning and NVR verification on large propulsion oxygen systems, and propulsion test stands and ground support equipment. . Many components are too large for ultrasonic agitation - necessary for effective aqueous cleaning and NVR sampling. . Test stand equipment must be cleaned prior to installation of test hardware. Many items must be cleaned by wipe or flush in situ where complete removal of a flammable solvent cannot be assured. The search for a replacement solvent for these applications is ongoing.
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Melnikov, Sergey M; Stein, Matthias
2018-03-15
CO 2 sequestration from anthropogenic resources is a challenge to the design of environmental processes at a large scale. Reversible chemical absorption by amine-based solvents is one of the most efficient methods of CO 2 removal. Molecular simulation techniques are very useful tools to investigate CO 2 binding by aqueous alkanolamine molecules for further technological application. In the present work, we have performed detailed atomistic molecular dynamics simulations of aqueous solutions of three prototype amines: monoethanolamine (MEA) as a standard, 3-aminopropanol (MPA), 2-methylaminoethanol (MMEA), and 4-diethylamino-2-butanol (DEAB) as potential novel CO 2 absorptive solvents. Solvent densities, radial distribution functions, cluster size distributions, hydrogen-bonding statistics, and diffusion coefficients for a full range of mixture compositions have been obtained. The solvent densities and diffusion coefficients from simulations are in good agreement with those in the experiment. In aqueous solution, MEA, MPA, and MMEA molecules prefer to be fully solvated by water molecules, whereas DEAB molecules tend to self-aggregate. In a range from 30/70-50/50 (w/w) alkanolamine/water mixtures, they form a bicontinuous phase (both alkanolamine and water are organized in two mutually percolating clusters). Among the studied aqueous alkanolamine solutions, the diffusion coefficients decrease in the following order MEA > MPA = MMEA > DEAB. With an increase of water content, the diffusion coefficients increase for all studied alkanolamines. The presented results are a first step for process-scale simulation and provide important qualitative and quantitative information for the design and engineering of efficient new CO 2 removal processes.
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Mesoscale Particle-Based Model of Electrophoresis
Giera, Brian; Zepeda-Ruiz, Luis A.; Pascall, Andrew J.; ...
2015-07-31
Here, we develop and evaluate a semi-empirical particle-based model of electrophoresis using extensive mesoscale simulations. We parameterize the model using only measurable quantities from a broad set of colloidal suspensions with properties that span the experimentally relevant regime. With sufficient sampling, simulated diffusivities and electrophoretic velocities match predictions of the ubiquitous Stokes-Einstein and Henry equations, respectively. This agreement holds for non-polar and aqueous solvents or ionic liquid colloidal suspensions under a wide range of applied electric fields.
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Molecular Weight Measurement of Biobased Furan Polyamides via Non-Aqueous Potentiometric Titration
2013-06-01
electromagnetic fields, all titrations were completed in a chemical hood, which acted as a Faraday cage (a shield used to blocks external static and...while using DMF as a solvent. Additionally, no Faraday cage was used in the experimental setup, so the titrations were conducted inside the chemical...monomer was becoming more soluble in glacial acetic acid and the amount of chlorobenzene had less of an effect on the solution properties (i.e
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Mesoscale Particle-Based Model of Electrophoresis
DOE Office of Scientific and Technical Information (OSTI.GOV)
Giera, Brian; Zepeda-Ruiz, Luis A.; Pascall, Andrew J.
Here, we develop and evaluate a semi-empirical particle-based model of electrophoresis using extensive mesoscale simulations. We parameterize the model using only measurable quantities from a broad set of colloidal suspensions with properties that span the experimentally relevant regime. With sufficient sampling, simulated diffusivities and electrophoretic velocities match predictions of the ubiquitous Stokes-Einstein and Henry equations, respectively. This agreement holds for non-polar and aqueous solvents or ionic liquid colloidal suspensions under a wide range of applied electric fields.
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Process and apparatus for solvent extraction of oil from oil-containing diatomite ore
DOE Office of Scientific and Technical Information (OSTI.GOV)
Karnofsky, G. B.
1980-12-16
A process for solvent extraction of oil from oil bearing diatomite ore and an apparatus for use therewith, wherein the ore is extracted by countercurrent decantation with a hydrocarbon solvent, solvent is recovered from the extract by multiple effect evaporation followed by stripping, and the spent diatomite is contacted with water to displace a major portion of the solvent therefrom, and solvent is recovered from the aqueous slurry of the spent diatomite by stripping with steam at superatmospheric pressure.
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Non-Aqueous Sol-Gel Synthesis of FePt Nanoparticles in the Absence of In Situ Stabilizers
Preller, Tobias; Knickmeier, Saskia; Porsiel, Julian Cedric; Temel, Bilal
2018-01-01
The synthesis of FePt nanocrystals is typically performed in an organic solvent at rather high temperatures, demanding the addition of the in situ stabilizers oleic acid and oleylamine to produce monomodal particles with well-defined morphologies. Replacing frequently-used solvents with organic media bearing functional moieties, the use of the stabilizers can be completely circumvented. In addition, various morphologies and sizes of the nanocrystals can be achieved by the choice of organic solvent. The kinetics of particle growth and the change in the magnetic behavior of the superparamagnetic FePt nanocrystals during the synthesis with a set of different solvents, as well as the resulting morphologies and stoichiometries of the nanoparticles were determined by powder X-ray diffraction (PXRD), small-angle X-ray scattering (SAXS), transmission electron microscopy (TEM), inductively coupled plasma optical emission spectroscopy (ICP-OES)/mass spectrometry (ICP-MS), and superconducting quantum interference device (SQUID) measurements. Furthermore, annealing of the as-prepared FePt nanoparticles led to the ordered L10 phase and, thus, to hard magnetic materials with varying saturation magnetizations and magnetic coercivities. PMID:29751508
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Deterred drug abuse using superabsorbent polymers.
Mastropietro, David J; Muppalaneni, Srinath; Omidian, Hossein
2016-11-01
This study aimed to determine whether selected superabsorbent polymers (SAPs) could be used as a suitable alternative to thwart extraction, filtration, and syringeability attempts for abuse. Many abuse-deterrent formulations (ADFs) rely on high molecular weight polymers such as poly(ethylene oxide) to provide crush and extraction resistance. However, these polymers suffer from slow dissolution kinetics, and are susceptible to a variety of abuse conditions. Several commercially available SAPs were evaluated for swelling behavior in extraction solvents, and tableting properties. Post-compaction abuse properties were evaluated by recoverable volume and syringeability after solvent extraction. Drug release and percent drug extraction were conducted using tramadol HCl as a model drug. Certain SAPs had the ability to rapidly imbibe solvent and effectively stop extraction processes in a variety of solvents, including water and water/alcohol mixtures. Tablets containing SAP and drug showed no effect on drug release in vitro. SAPs possess adequate properties for tableting, and maintain their high and fast swelling properties after compaction. The fast and extensive interactions of SAPs with aqueous medium are a major advantage over non-crosslinked high molecular weight viscosifying agents such as poly(ethylene oxide).
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Application of liquid-liquid interactions with single-walled carbon nanotubes
NASA Astrophysics Data System (ADS)
Wang, Randy Kai-Wei
This study covers three important research topics related to the application of liquid-liquid interaction with single-walled carbon nanotubes (SWNTs). The first topic describes the removal of SWNT bundles from liquid suspensions of nanotubes. The key to this work includes the use of liquid-liquid interfaces to trap the SWNT bundles due to the free energy change of the system during the process. SWNTs pack into crystalline ropes that form bundles due to strong van der Waals attraction. Bundling diminishes mechanical and electronic properties because it could interrupt the electronic structure of the nanotubes. Also, the electronic devices based on as-grown nanotubes, which contains a mixture of individual nanotubes and nanotube bundles, make the electrical response unpredictable. We developed a new simple process to remove bundles by liquid-liquid interaction. SWNTs bundles are trapped at the interface because bundles stabilize the emulsions. Eliminating the use of ultracentrifugation to remove SWNT bundles enables large-scale production with reduced production costs and time savings. The second topic presented the swelling effect of the surfactant layer surrounding SWNTs with nonpolar solvents. Solvatochromic shifts in the absorbance and fluorescence spectra are observed when surfactant-stabilized aqueous SWNT suspensions are mixed with immiscible organic solvents. When aqueous surfactant-suspended SWNTs are mixed with certain solvents, the spectra closely match the peaks for SWNTs dispersed in only that solvent. These spectral changes suggest the hydrophobic region of the micelle surrounding SWNTs swells with the organic solvent when mixed. The solvatochromic shifts of the aqueous SWNT suspensions are reversible once the solvent evaporates. However, some surfactant-solvent systems show permanent changes to the fluorescence emission intensity after exposure to the organic solvent. The intensity of some large diameter SWNT (n, m) types increase by more than 175%. These differences are attributed to surfactant reorganization, which can improve nanotube coverage, resulting in decreased exposure to quenching mechanisms from the aqueous phase. The third topic describes the further study of the solvatochromism of the SWNTs. Since SWNTs are encapsulated with microenvironments of nonpolar solvents, it provides a new method to measure the photophysical properties of nanotubes in environments with known properties. Fluorescence and absorbance spectra of SWNTs show solvatochromic shifts in 16 nonpolar solvents, which are proportional to the solvent induction polarization. The photophysical properties of SWNTs were used to determine the relationship between the longitudinal polarizability and other nanotube properties, alpha11,|| ∝ 1/(R2E11 3). (Full text of this dissertation may be available via the University of Florida Libraries web site. Please check http://www.uflib.ufl.edu/etd.html)
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Carrillo, Carlos A; Nypelö, Tiina; Rojas, Orlando J
2016-03-14
A route for the compatibilization of aqueous dispersions of cellulose nanofibrils (CNFs) with a non-polar polymer matrix is proposed to overcome a major challenge in CNF-based material synthesis. Non-ionic surfactants were used in CNF aqueous dispersions equilibrated with an organic phase (for demonstration, a polystyrene solution, PS, was used). Stable water-in-oil-in-water (W/O/W) double emulsions were produced as a result of the compromise between composition and formulation variables. Most remarkably, the proposed route for CNF integration with hydrophobic polymers removed the need for drying or solvent-exchange of the CNF aqueous dispersion prior to processing. The rheological behavior of the double emulsions showed strong shear thinning behavior and facilitated CNF-PS co-mixing in solid nanofibers upon electrospinning. The morphology and thermal properties of the resultant nanofibers revealed that CNFs were efficiently integrated in the hydrophobic matrix which was consistent with the high interfacial area of the precursor double emulsion. In addition, the morphology and quality of the composite nanofibers can be controlled by the conductivity (ionic strength) of the CNF dispersion. Overall, double emulsion systems are proposed as a novel, efficient and scalable platform for CNF co-processing with non-polar systems and they open up the possibility for the redispersion of CNFs after removal of the organic phase.
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Sugaya, Sari; Yamada, Masumi; Hori, Ayaka; Seki, Minoru
2013-01-01
In this study, a microfluidic process is proposed for preparing monodisperse micrometer-sized hydrogel beads. This process utilizes non-equilibrium aqueous droplets formed in a polar organic solvent. The water-in-oil droplets of the hydrogel precursor rapidly shrunk owing to the dissolution of water molecules into the continuous phase. The shrunken and condensed droplets were then gelled, resulting in the formation of hydrogel microbeads with sizes significantly smaller than the initial droplet size. This study employed methyl acetate as the polar organic solvent, which can dissolve water at 8%. Two types of monodisperse hydrogel beads—Ca-alginate and chitosan—with sizes of 6–10 μm (coefficient of variation < 6%) were successfully produced. In addition, we obtained hydrogel beads with non-spherical morphologies by controlling the degree of droplet shrinkage at the time of gelation and by adjusting the concentration of the gelation agent. Furthermore, the encapsulation and concentration of DNA molecules within the hydrogel beads were demonstrated. The process presented in this study has great potential to produce small and highly concentrated hydrogel beads that are difficult to obtain by using conventional microfluidic processes. PMID:24396529
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Sugaya, Sari; Yamada, Masumi; Hori, Ayaka; Seki, Minoru
2013-01-01
In this study, a microfluidic process is proposed for preparing monodisperse micrometer-sized hydrogel beads. This process utilizes non-equilibrium aqueous droplets formed in a polar organic solvent. The water-in-oil droplets of the hydrogel precursor rapidly shrunk owing to the dissolution of water molecules into the continuous phase. The shrunken and condensed droplets were then gelled, resulting in the formation of hydrogel microbeads with sizes significantly smaller than the initial droplet size. This study employed methyl acetate as the polar organic solvent, which can dissolve water at 8%. Two types of monodisperse hydrogel beads-Ca-alginate and chitosan-with sizes of 6-10 μm (coefficient of variation < 6%) were successfully produced. In addition, we obtained hydrogel beads with non-spherical morphologies by controlling the degree of droplet shrinkage at the time of gelation and by adjusting the concentration of the gelation agent. Furthermore, the encapsulation and concentration of DNA molecules within the hydrogel beads were demonstrated. The process presented in this study has great potential to produce small and highly concentrated hydrogel beads that are difficult to obtain by using conventional microfluidic processes.
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Mass Transfer And Hydraulic Testing Of The V-05 And V-10 Contactors With The Next Generation Solvent
DOE Office of Scientific and Technical Information (OSTI.GOV)
Herman, D. T.; Duignan, M. R.; Williams, M. R.
The Modular Caustic Side Solvent Extraction (CSSX) Unit (MCU) facility is actively pursuing the transition from the current BOBCalixC6 based solvent to the Next Generation Solvent (NGS)-MCU solvent. To support this integration of NGS into the MCU facilities, Savannah River Remediation (SRR) requested that Savannah River National Laboratory (SRNL) perform testing of a blend of the NGS (MaxCalix based solvent) with the current solvent (BOBCalixC6 based solvent) for the removal of cesium (Cs) from the liquid salt waste stream. This testing differs from prior testing by utilizing a blend of BOBCalixC6 based solvent and the NGS with the full (0.05more » M) concentration of the MaxCalix as well as a new suppressor, tris(3,7dimethyloctyl) guanidine. Single stage tests were conducted using the full size V-05 and V-10 centrifugal contactors installed at SRNL. These tests were designed to determine the mass transfer and hydraulic characteristics with the NGS solvent blended with the projected heel of the BOBCalixC6 based solvent that will exist in MCU at time of transition. The test program evaluated the amount of organic carryover and the droplet size of the organic carryover phases using several analytical methods. Stage efficiency and mass distribution ratios were determined by measuring Cs concentration in the aqueous and organic phases during single contactor testing. The nominal cesium distribution ratio, D(Cs) measured for extraction ranged from 37-60. The data showed greater than 96% stage efficiency for extraction. No significant differences were noted for operations at 4, 8 or 12 gpm aqueous salt simulant feed flow rates. The first scrub test (contact with weak caustic solution) yielded average scrub D(Cs) values of 3.3 to 5.2 and the second scrub test produced an average value of 1.8 to 2.3. For stripping behavior, the “first stage” D Cs) values ranged from 0.04 to 0.08. The efficiency of the low flow (0.27 gpm aqueous) was calculated to be 82.7%. The Spreadsheet Algorithm for Stagewise Solvent Extraction (SASSE) predicted equivalent DF for MCU from this testing is greater than 3,500 assuming 95% efficiency during extraction and 80% efficiency during scrub and strip. Hydraulically, the system performed very well in all tests. Target flows were easily obtained and stable throughout testing. Though some issues were encountered with plugging in the coalescer, they were not related to the solvent. No hydraulic upsets due to the solvent were experienced during any of the tests conducted. The first extraction coalescer element used in testing developed high pressure drop that made it difficult to maintain the target flow rates. Analysis showed an accumulation of sodium aluminosilicate solids. The coalescer was replaced with one from the same manufacturer’s lot and pressure drop was no longer an issue. Concentrations of Isopar™ L and Modifier were measured using semi-volatile organic analysis (SVOA) and high performance liquid chromatography (HPLC) to determine the amount of solvent carryover. For low-flow (0.27 gpm aqueous) conditions in stripping, SVOA measured the Isopar™ L post-contactor concentration to be 25 mg/L, HPLC measured 39 mg/L of Modifier. For moderate-flow (0.54 gpm aqueous) conditions, SVOA measured the Isopar™ L postcontactor to be ~69 mg/L, while the HPLC measured 56 mg/L for Modifier. For high-flow (0.8 gpm aqueous) conditions, SVOA measured the Isopar™ L post-contactor to be 39 mg/L. The post-coalescer (pre-decanter) measurements by SVOA for Isopar™ L were all less than the analysis detection limit of 10 mg/L. The HPLC measured 18, 22 and 20 mg/L Modifier for the low, medium, and high-low rates respectively. In extraction, the quantity of pre-coalescer Isopar™ L carryover measured by SVOA was ~280-410 mg/L at low flow (4 gpm aqueous), ~400-450 mg/L at moderate flow (8 gpm aqueous), and ~480 mg/L at high flow (12 gpm aqueous). The amount of post coalescer (pre-decanter) Isopar™ L carryover measured by SVOA was less than 45 mg/L for all flow rates. HPLC results for Modifier were 182, 217 and 222 mg/L for the post-contactor low, medium and high flow rates. The post-coalescer (pre-decanter) samples were measured to contain 12, 10 and 22 mg/L Modifier for the low, medium, and high flow rates. The carryover results and droplet size measurements were used to determine the decanter performance utilizing the decanter model developed by the ARES Corporation. Results show for the targeted salt flow rate of approximately 8 gpm, that over 93% of the solvent carryover from stripping is predicted to be recovered and over 96% solvent carryover from extraction is predicted to be recovered. This translates to a predicted solvent carryover of <3 ppm from stripping and <20 ppm solvent carryover from extraction. This projected performance at MCU is expected to be well within the operating limits and the historical performance for the baseline BOBCalixC6 based solvent. Droplet-size data obtained by MicroTrac™ S3400 analyzer consistently shows that the droplet size post-oalescer is significantly greater than the post-contactor or pre-coalescer samples. Increased flow rates did not show a consistent impact to the droplet size results. For the extraction testing, droplet size analysis showed that the post-contactor and pre-coalescer samples were essentially the same. The mean droplet sizes post-coalescer were less than the mean droplet sizes pre-coalescer with a very slight upward trend in the mean droplet size as the flow rate was increased. This result is probably due to the method of sampling. The larger post-coalescer drops immediately rise to the surface after leaving the coalescer element. The downstream sampling point was horizontally in-line with the element and therefore would only capture those organic droplets well mixed in the flowing aqueous stream.« less
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Modeling the absorption spectrum of the permanganate ion in vacuum and in aqueous solution
NASA Astrophysics Data System (ADS)
Olsen, Jógvan Magnus Haugaard; Hedegård, Erik Donovan
The absorption spectrum of the MnO$_{4}$$^{-}$ ion has been a test-bed for quantum-chemical methods over the last decades. Its correct description requires highly-correlated multiconfigurational methods, which are incompatible with the inclusion of finite-temperature and solvent effects due to their high computational demands. Therefore, implicit solvent models are usually employed. Here we show that implicit solvent models are not sufficiently accurate to model the solvent shift of MnO$_{4}$$^{-}$, and we analyze the origins of their failure. We obtain the correct solvent shift for MnO$_{4}$$^{-}$ in aqueous solution by employing the polarizable embedding (PE) model combined with a range-separated complete active space short-range density functional theory method (CAS-srDFT). Finite-temperature effects are taken into account by averaging over structures obtained from ab initio molecular dynamics simulations. The explicit treatment of finite-temperature and solvent effects facilitates the interpretation of the bands in the low-energy region of the MnO$_{4}$$^{-}$ absorption spectrum, whose assignment has been elusive.
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NASA Astrophysics Data System (ADS)
Das, Koyeli; Roy, Milan Chandra; Rajbanshi, Biplab; Roy, Mahendra Nath
2017-11-01
Qualitative and quantitative analysis of molecular interaction prevailing in tyrosine and tryptophan in aqueous solution of vitamin C have been probed by thermophysical properties. The apparent molar volume (ϕV), viscosity B-coefficient, molal refraction (RM) of tyrosine and tryptophan have been studied in aqueous vitamin C solutions at diverse temperatures via Masson equation which deduced solute-solvent and solute-solute interactions, respectively. Spectroscopic study along with physicochemical and computational techniques provides lots of interesting and highly significant insights of the model biological systems. The overall results established strong solute-solvent interactions between studied amino acids and vitamin C mixture in the ternary solutions.
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Enthalpy characteristics of L-proline dissolution in certain water-organic mixtures at 298.15 K
NASA Astrophysics Data System (ADS)
Badelin, V. G.; Smirnov, V. I.
2017-01-01
A thermochemical study of the processes of L-proline dissolution in aqueous solutions of acetonitrile, 1,4-dioxane, acetone, dimethyl sulfoxide, nitromethane and tetrahydrofuran at T = 298.15 K in the range of organic solvent concentrations x2 = 0-0.25 mole fractions is performed. Standard values of the enthalpies of solution and transfer of L-proline from water to mixed solvent, and the enthalpy coefficients of pairwise interactions between L-proline and molecules of organic solvents, are calculated. The effect the composition of a water-organic mixture and the structure of organic solvents have on the enthalpy characteristics of L-proline dissolution and transfer is examined. The effect the energy properties of intermolecular interactions between components of a mixed solvent has on the intermolecular interactions between L-proline and molecules of cosolvent is estimated. The correlation between the enthalpy characteristics of L-proline dissolution and electron-donor properties of organic cosolvent in aqueous solutions is determined.
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Zeng, Yun; Liu, Gang; Ma, Ying; Chen, Xiaoyuan; Ito, Yoichiro
2012-01-01
A new series of organic-high ionic strength aqueous two-phase solvents systems was designed for separation of highly polar compounds by spiral high-speed counter-current chromatography. A total of 21 solvent systems composed of 1-butanol-ethanol-saturated ammonium sulfate-water at various volume ratios are arranged according to an increasing order of polarity. Selection of the two-phase solvent system for a single compound or a multiple sample mixture can be achieved by two steps of partition coefficient measurements using a graphic method. The capability of the method is demonstrated by optimization of partition coefficient for seven highly polar samples including tartrazine (K=0.77), tryptophan (K=1.00), methyl green (K= 0.93), tyrosine (0.81), metanephrine (K=0.89), tyramine (K=0.98), and normetanephrine (K=0.96). Three sulfonic acid components in D&C Green No. 8 were successfully separated by HSCCC using the graphic selection of the two-phase solvent system. PMID:23467197
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Zhang, Wei-Nong; Liu, Da-Chuan
2005-01-01
A new process for the preparation of soybean protein concentrate (SPC) by directly extracting full-fat soy flour with a mixture of hexane and aqueous ethanol was established. Compared with conventional methods, it has some advantages, such as saving energy and reducing protein denaturation caused by heat action during solvent recovery, because this process saves one step of solvent recovery. The effects of aqueous ethanol concentration and the mixure ratio (hexane to ethanol) on the degree of protein denaturation and product quality were investigated, on the basis of which the orthogonal tests were performed. The optimum technical parameters were obtained by analyzing the results of the orthogonal tests with statistical methods. We found that SPC can be obtained by extracting full-fat soy flour under the following conditions: mixture ratio hexane: 90% ethanol, 9:1, v/v; extraction temperature, 45 degrees C; ratio of solid to solvents, (1:2 w/v); and 5 repeated extractions (15 min each time). The results of quality analysis showed that solubility of the product was improved significantly [nitrogen solubility index (NSI) 46.6%] compared with that for ethanol washing of protein concentrate (NSI 8.7%).
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Moyer, Bruce A.; Sachleben, Richard A.; Bonnesen, Peter V.; Presley, Derek J.
2001-01-01
A solvent composition and corresponding method for extracting cesium (Cs) from aqueous neutral and alkaline solutions containing Cs and perhaps other competing metal ions is described. The method entails contacting an aqueous Cs-containing solution with a solvent consisting of a specific class of lipophilic calix[4]arene-crown ether extractants dissolved in a hydrocarbon-based diluent containing a specific class of alkyl-aromatic ether alcohols as modifiers. The cesium values are subsequently recovered from the extractant, and the solvent subsequently recycled, by contacting the Cs-containing organic solution with an aqueous stripping solution. This combined extraction and stripping method is especially useful as a process for removal of the radionuclide cesium-137 from highly alkaline waste solutions which are also very concentrated in sodium and potassium. No pre-treatment of the waste solution is necessary, and the cesium can be recovered using a safe and inexpensive stripping process using water, dilute (millimolar) acid solutions, or dilute (millimolar) salt solutions. An important application for this invention would be treatment of alkaline nuclear tank wastes. Alternatively, the invention could be applied to decontamination of acidic reprocessing wastes containing cesium-137.
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Rubinstein, Alexander; Sherman, Simon
The dielectric properties of the polar solvent on the protein-solvent interface at small intercharge distances are still poorly explored. To deconvolute this problem and to evaluate the pair-wise electrostatic interaction (PEI) energies of the point charges located at the protein-solvent interface we used a nonlocal (NL) electrostatic approach along with a static NL dielectric response function of water. The influence of the aqueous solvent microstructure (determined by a strong nonelectrostatic correlation effect between water dipoles within the orientational Debye polarization mode) on electrostatic interactions at the interface was studied in our work. It was shown that the PEI energies can be significantly higher than the energies evaluated by the classical (local) consideration, treating water molecules as belonging to the bulk solvent with a high dielectric constant. Our analysis points to the existence of a rather extended, effective low-dielectric interfacial water shell on the protein surface. The main dielectric properties of this shell (effective thickness together with distance- and orientation-dependent dielectric permittivity function) were evaluated. The dramatic role of this shell was demonstrated when estimating the protein association rate constants.
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Li, Hui; Chen, Bo; Zhang, Zhaohui; Yao, Shouzhuo
2004-06-17
A new focused microwave-assisted solvent extraction method using water as solvent has been developed for leaching geniposidic and chlorogenic acids from Eucommia ulmodies Oliv. The extraction procedures were optimized using a two indexes orthogonal experimental design and graphical analysis, by varying irradiation time, solvent volume, solvent composition and microwave power. The optimum extraction conditions were obtained: for geniposidic acid, 50% micorwave power, 40s irradiation, and 80% (v/v) aqueous methanol as extraction solvent (20mlg(-1) sample); and for chlorogenic acid, 50% micorwave power, 30s irradiation, and 20% aqueous methanol (20mlg(-1) sample). The composition of the extraction solvent was optimized and can be directly used as the mobile phase in the HPLC separation. Quantification of organic acids was done by HPLC at room temperature using Spherigel C(18) chromatographic column (250 mm x4.6 mm , i.d. 5mum), the methanol:water:acetic acid (20:80:1.0, v/v) mobile phase and UV detection at 240nm. The R.S.D. of the extraction process for geniposidic and chlorogenic acid were 3.8 and 4.1%, respectively.
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Dialysis Extraction for Chromatography
NASA Technical Reports Server (NTRS)
Jahnsen, V. J.
1985-01-01
Chromatographic-sample pretreatment by dialysis detects traces of organic contaminants in water samples analyzed in field with minimal analysis equipment and minimal quantities of solvent. Technique also of value wherever aqueous sample and solvent must not make direct contact.
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Replacement Technologies for Precision Cleaning of Aerospace Hardware for Propellant Service
NASA Technical Reports Server (NTRS)
Beeson, Harold; Kirsch, Mike; Hornung, Steven; Biesinger, Paul
1997-01-01
The NASA White Sands Test Facility (WSTF) is developing cleaning and verification processes to replace currently used chlorofluorocarbon-l13- (CFC-113-) based processes. The processes being evaluated include both aqueous- and solvent-based techniques. Replacement technologies are being investigated for aerospace hardware and for gauges and instrumentation. This paper includes the findings of investigations of aqueous cleaning and verification of aerospace hardware using known contaminants, such as hydraulic fluid and commonly used oils. The results correlate nonvolatile residue with CFC 113. The studies also include enhancements to aqueous sampling for organic and particulate contamination. Although aqueous alternatives have been identified for several processes, a need still exists for nonaqueous solvent cleaning, such as the cleaning and cleanliness verification of gauges used for oxygen service. The cleaning effectiveness of tetrachloroethylene (PCE), trichloroethylene (TCE), ethanol, hydrochlorofluorocarbon 225 (HCFC 225), HCFC 141b, HFE 7100(R), and Vertrel MCA(R) was evaluated using aerospace gauges and precision instruments and then compared to the cleaning effectiveness of CFC 113. Solvents considered for use in oxygen systems were also tested for oxygen compatibility using high-pressure oxygen autogenous ignition and liquid oxygen mechanical impact testing.
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Development of CFC-Free Cleaning Processes at the NASA White Sands Test Facility
NASA Technical Reports Server (NTRS)
Beeson, Harold; Kirsch, Mike; Hornung, Steven; Biesinger, Paul
1995-01-01
The NASA White Sands Test Facility (WSTF) is developing cleaning and verification processes to replace currently used chlorofluorocarbon-113- (CFC-113-) based processes. The processes being evaluated include both aqueous- and solvent-based techniques. The presentation will include the findings of investigations of aqueous cleaning and verification processes that are based on a draft of a proposed NASA Kennedy Space Center (KSC) cleaning procedure. Verification testing with known contaminants, such as hydraulic fluid and commonly used oils, established correlations between nonvolatile residue and CFC-113. Recoveries ranged from 35 to 60 percent of theoretical. WSTF is also investigating enhancements to aqueous sampling for organics and particulates. Although aqueous alternatives have been identified for several processes, a need still exists for nonaqueous solvent cleaning, such as the cleaning and cleanliness verification of gauges used for oxygen service. The cleaning effectiveness of tetrachloroethylene (PCE), trichloroethylene (TCE), ethanol, hydrochlorofluorocarbon-225 (HCFC-225), tert-butylmethylether, and n-Hexane was evaluated using aerospace gauges and precision instruments and then compared to the cleaning effectiveness of CFC-113. Solvents considered for use in oxygen systems were also tested for oxygen compatibility using high-pressure oxygen autoignition and liquid oxygen mechanical impact testing.
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NASA Astrophysics Data System (ADS)
Weber, Waldemar; Wagner, Ralf; Streipert, Benjamin; Kraft, Vadim; Winter, Martin; Nowak, Sascha
2016-02-01
The electrochemical aging of commercial non-aqueous lithium hexafluorophosphate (LiPF6)/organic carbonate solvent based lithium ion battery electrolyte has been investigated in view of the formation of ionic and non-ionic alkylated phosphates. Subject was a solvent mixture of ethylene carbonate/ethyl methyl carbonate EC:EMC (1:1, by wt.) with 1 M LiPF6 (LP50 Selectilyte™, BASF). The analysis was carried out by ion chromatography coupled with electrospray ionization mass spectrometry (ESI-MS) for ionic compounds and (headspace) gas chromatography mass spectrometry ((HS)-GC-MS) for non-ionic compounds. The electrochemical aging was performed by galvanostatic charge/discharge cycling and potentiostatic experiments with LiNi0.5Mn1.5O4 (LMNO) as cathode material at increased cut-off potentials (>4.5 V vs. Li/Li+). A strong dependence of the formation of organophosphates on the applied electrode potential was observed and investigated by quantitative analysis of the formed phosphates. In addition, new possible ;fingerprint; compounds for describing the electrolyte status were investigated and compared to existing compounds.
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Precision Cleaning of Oxygen Systems and Components
NASA Technical Reports Server (NTRS)
McLaughlin, Russell
2009-01-01
Currently, NASA uses Dichloropentafluoropropane (HCFC-225), a Class II ozone depleting substance (ODs), to clean contaminated oxygen systems. Starting in 20 15, the Montreal Protocols and Clean Air Act prohibit the production and importation of all hydrochlorofluorocarbons (HCFC), except for limited use in refrigeration applications. Thus, a new non-ozone depleting solvent needs to be developed for use in cleaning. Optimally, such a solvent should also be environmentally benign or green to avoid needing to replace the new solvent with yet another solvent in the future due to other environmental concerns. Work for the first year consisted of two parts. The first part was developing a method of testing the cleaning efficiency of potential solvents. Stainless steel coupons were contaminated with a known weight of various contaminants and contaminant combinations and then immersed in solvent for ten minutes. The coupons were then removed and dried in an oven until all solvent had evaporated. Once dry, the coupons were weighed and the mass of the non-volatile residue (NVR) left on the coupon was determined. The cleaning efficiency of the solvents is reported as percent cleaning, with 100% cleaning being zero NVR left on the test coupon. The second half of the first goal was to use the develop method to perform baseline testing on current solvents. The second part of the work was to begin exploring alternative cleaning solvents. A variety of hydrofluorocarbons (HFCs) were tested. Preliminary testing was also performed with ionic liquids and aqueous surfactant solutions. Once potential solvents were identified, an analysis of the performance and environmental characteristics of each was to be conducted. Four contaminants were specified for use in testing. These are Mil-Spec-H-5606 (5606), a hydraulic fluid, Mil-H-83282B (83282), another hydraulic fluid, diethylhexyl sebacate (Sebacate), and WD-40. The structures of these contaminants are all similar, with long aliphatic hydrocarbon chains of lengths between fifteen and fifty. Contaminants were tested both individually and in combination. All combinations were done with equal weights of the constituent contaminants.
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Palladium in Non-Aqueous Solvents. Formation, Stability, and Film Forming Properties.
1987-07-14
data reported by Furlong7 in which high valent cations induced flocculation faster than monovalent cations. Addition of water to the colloid induced...reactlons Lf acetone with metal atoms. A number of radiolysis studies -f metal o in water -acetone solutions indicate that organ.c rad 2as ic trinsfer...electrons to the particles which act as electron reservoirs anc "an 7enawe as catalysts for water reduction).2’ (CH ) _OH ’,Ag) ZHA 32 If free radicals
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NASA Astrophysics Data System (ADS)
Farahmand, Farnaz; Ghasemzadeh, Bahar; Naseri, Abdolhossein
2018-01-01
An air assisted liquid-liquid microextraction by applying the solidification of a floating organic droplet method (AALLME-SFOD) coupled with a multivariate calibration method, namely partial least squares (PLS), was introduced for the fast and easy determination of Atenolol (ATE), Propanolol (PRO) and Carvedilol (CAR) in biological samples via a spectrophotometric approach. The analytes would be extracted from neutral aqueous solution into 1-dodecanol as an organic solvent, using AALLME. In this approach a low-density solvent with a melting point close to room temperature was applied as the extraction solvent. The emulsion was immediately formed by repeatedly pulling in and pushing out the aqueous sample solution and extraction solvent mixture via a 10-mL glass syringe for ten times. After centrifugation, the extractant droplet could be simply collected from the aqueous samples by solidifying the emulsion at a lower than the melting point temperature. In the next step, analytes were back extracted simultaneously into the acidic aqueous solution. Derringer and Suich multi-response optimization were utilized for simultaneous optimizing the parameters of three analytes. This method incorporates the benefits of AALLME and dispersive liquid-liquid microextraction considering the solidification of floating organic droplets (DLLME-SFOD). Calibration graphs under optimized conditions were linear in the range of 0.30-6.00, 0.32-2.00 and 0.30-1.40 μg mL- 1 for ATE, CAR and PRO, respectively. Other analytical parameters were obtained as follows: enrichment factors (EFs) were found to be 11.24, 16.55 and 14.90, and limits of detection (LODs) were determined to be 0.09, 0.10 and 0.08 μg mL- 1 for ATE, CAR and PRO, respectively. The proposed method will require neither a highly toxic chlorinated solvent for extraction nor an organic dispersive solvent in the application process; hence, it is more environmentally friendly.
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Farahmand, Farnaz; Ghasemzadeh, Bahar; Naseri, Abdolhossein
2018-01-05
An air assisted liquid-liquid microextraction by applying the solidification of a floating organic droplet method (AALLME-SFOD) coupled with a multivariate calibration method, namely partial least squares (PLS), was introduced for the fast and easy determination of Atenolol (ATE), Propanolol (PRO) and Carvedilol (CAR) in biological samples via a spectrophotometric approach. The analytes would be extracted from neutral aqueous solution into 1-dodecanol as an organic solvent, using AALLME. In this approach a low-density solvent with a melting point close to room temperature was applied as the extraction solvent. The emulsion was immediately formed by repeatedly pulling in and pushing out the aqueous sample solution and extraction solvent mixture via a 10-mL glass syringe for ten times. After centrifugation, the extractant droplet could be simply collected from the aqueous samples by solidifying the emulsion at a lower than the melting point temperature. In the next step, analytes were back extracted simultaneously into the acidic aqueous solution. Derringer and Suich multi-response optimization were utilized for simultaneous optimizing the parameters of three analytes. This method incorporates the benefits of AALLME and dispersive liquid-liquid microextraction considering the solidification of floating organic droplets (DLLME-SFOD). Calibration graphs under optimized conditions were linear in the range of 0.30-6.00, 0.32-2.00 and 0.30-1.40μg mL -1 for ATE, CAR and PRO, respectively. Other analytical parameters were obtained as follows: enrichment factors (EFs) were found to be 11.24, 16.55 and 14.90, and limits of detection (LODs) were determined to be 0.09, 0.10 and 0.08μg mL -1 for ATE, CAR and PRO, respectively. The proposed method will require neither a highly toxic chlorinated solvent for extraction nor an organic dispersive solvent in the application process; hence, it is more environmentally friendly. Copyright © 2017 Elsevier B.V. All rights reserved.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Idem, R.; Wilson, M.; Tontiwachwuthikul, P.
2006-04-12
Evaluations of the benefits of using a mixed MEA/MDEA solvent for CO{sub 2} capture in terms of the heat requirement for solvent regeneration, lean and rich loadings, CO{sub 2} production, and solvent stability were performed by comparing the performance of aqueous 5 kmol/m{sup 3} MEA with that of an aqueous 4:1 molar ratio MEA/MDEA blend of 5 kmol/ml total amine concentration as a function of the operating time. The tests were performed using two pilot CO{sub 2} capture plants of the International Test Centre for CO{sub 2} Capture (ITC), which provided two different sources and compositions of flue gas. Themore » University of Regina CO{sub 2} plant (UR unit) processes flue gas from the combustion of natural gas while the Boundary Dam CO{sub 2} plant (BD unit) processes flue gas from a coal-fired electric power station. The results show that a huge heat-duty reduction can be achieved by using a mixed MEA/MDEA solution instead of a single MEA solution in an industrial environment of a CO{sub 2} capture plant. However, this benefit is dependent on whether the chemical stability of the solvent can be maintained.« less
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Aladaghlo, Zolfaghar; Fakhari, Alireza; Behbahani, Mohammad
2016-10-01
In this work, an efficient sample preparation method termed solvent-assisted dispersive solid-phase extraction was applied. The used sample preparation method was based on the dispersion of the sorbent (benzophenone) into the aqueous sample to maximize the interaction surface. In this approach, the dispersion of the sorbent at a very low milligram level was achieved by inserting a solution of the sorbent and disperser solvent into the aqueous sample. The cloudy solution created from the dispersion of the sorbent in the bulk aqueous sample. After pre-concentration of the butachlor, the cloudy solution was centrifuged and butachlor in the sediment phase dissolved in ethanol and determined by gas chromatography with flame ionization detection. Under the optimized conditions (solution pH = 7.0, sorbent: benzophenone, 2%, disperser solvent: ethanol, 500 μL, centrifuged at 4000 rpm for 3 min), the method detection limit for butachlor was 2, 3 and 3 μg/L for distilled water, waste water, and urine sample, respectively. Furthermore, the preconcentration factor was 198.8, 175.0, and 174.2 in distilled water, waste water, and urine sample, respectively. Solvent-assisted dispersive solid-phase extraction was successfully used for the trace monitoring of butachlor in urine and waste water samples. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Curtis, C.W.; Chander, S.; Gutterman, C.
Liquefaction experiments were undertaken using subbituminous Black Thunder mine coal to observe the effects of aqueous SO{sub 2} coal beneficiation and the introduction of various coal swelling solvents and catalyst precursors. Aqueous SO{sub 2} beneficiation of Black Thunder coal removed alkali metals and alkaline earth metals, increased the sulfur content and increased the catalytic liquefaction conversion to THF solubles compared to untreated Black Thunder coal. The liquefaction solvent had varying effects on coal conversion, depending upon the type of solvent added. The hydrogen donor solvent, dihydroanthracene, was most effective, while a coal-derived Wilsonville solvent promoted more coal conversion than didmore » relatively inert 1-methylnaphthalene. Swelling of coal with hydrogen bonding solvents tetrahydrofuran (THF), isopropanol, and methanol, prior to reaction resulted in increased noncatalytic conversion of both untreated and SO{sub 2} treated Black Thunder coals, while dimethylsulfoxide (DMSO), which was absorbed more into the coal than any other swelling solvent, was detrimental to coal conversion. Swelling of SO{sub 2} treated coal before liquefaction resulted in the highest coal conversions; however, the untreated coal showed the most improvements in catalytic reactions when swelled in either THF, isopropanol, or methanol prior to liquefaction. The aprotic solvent DMSO was detrimental to coal conversion.« less
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NASA Astrophysics Data System (ADS)
Nakayama, Akira; Arai, Gaku; Yamazaki, Shohei; Taketsugu, Tetsuya
2013-12-01
On-the-fly excited-state quantum mechanics/molecular mechanics molecular dynamics (QM/MM-MD) simulations of thymine in aqueous solution are performed to investigate the role of solvent water molecules on the nonradiative deactivation process. The complete active space second-order perturbation theory (CASPT2) method is employed for a thymine molecule as the QM part in order to provide a reliable description of the excited-state potential energies. It is found that, in addition to the previously reported deactivation pathway involving the twisting of the C-C double bond in the pyrimidine ring, another efficient deactivation pathway leading to conical intersections that accompanies the out-of-plane displacement of the carbonyl group is observed in aqueous solution. Decay through this pathway is not observed in the gas phase simulations, and our analysis indicates that the hydrogen bonds with solvent water molecules play a key role in stabilizing the potential energies of thymine in this additional decay pathway.
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Shaikh, Vasim R; Terdale, Santosh S; Ahamad, Abdul; Gupta, Gaurav R; Dagade, Dilip H; Hundiwale, Dilip G; Patil, Kesharsingh J
2013-12-19
The osmotic coefficient measurements for binary aqueous solutions of 2,2,2-cryptand (4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8] hexacosane) in the concentration range of ~0.009 to ~0.24 mol·kg(-1) and in ternary aqueous solutions containing a fixed concentration of 2,2,2-cryptand of ~0.1 mol·kg(-1) with varying concentration of KBr (~0.06 to ~0.16 mol·kg(-1)) have been reported at 298.15 K. The diamine gets hydrolyzed in aqueous solutions and needs proper approach to obtain meaningful thermodynamic properties. The measured osmotic coefficient values are corrected for hydrolysis and are used to determine the solvent activity and mean ionic activity coefficients of solute as a function of concentration. Strong ion-pair formation is observed, and the ion-pair dissociation constant for the species [CrptH](+)[OH(-)] is reported. The excess and mixing thermodynamic properties (Gibbs free energy, enthalpy, and entropy changes) have been obtained using the activity data from this study and the heat data reported in the literature. Further, the data are utilized to compute the partial molal entropies of solvent and solute at finite as well as infinite dilution of 2,2,2-cryptand in water. The concentration dependent non-linear enthalpy-entropy compensation effect has been observed for the studied system, and the compensation temperature along with entropic parameter are reported. Using solute activity coefficient data in ternary solutions, the transfer Gibbs free energies for transfer of the cryptand from water to aqueous KBr as well as transfer of KBr from water to aqueous cryptand were obtained and utilized to obtain the salting constant (ks) and thermodynamic equilibrium constant (log K) values for the complex (2,2,2-cryptand:K(+)) at 298.15 K. The value of log K = 5.8 ± 0.1 obtained in this work is found to be in good agreement with that reported by Lehn and Sauvage. The standard molar entropy for complexation is also estimated for the 2,2,2-cryptand-KBr complex in aqueous medium.
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Process and apparatus for solvent extraction of oil from oil-containing diatomite ore
DOE Office of Scientific and Technical Information (OSTI.GOV)
Karnofsky, G.B.
1979-09-11
A process is described for solvent extraction of oil-bearing diatomite ore. An apparatus is provided for use therewith, wherein the ore is extracted by countercurrent decantation with a hydrocarbon solvent. The solvent is recovered from the extract by multiple effect evaporation followed by stripping, and the spent diatomite is contacted with water to displace a major portion of the solvent therefrom. The solvent is recovered from the aqueous slurry of the spent diatomite by stripping with steam at superatmospheric pressure. 17 claims.
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Polymer-assisted aqueous deposition of metal oxide films
Li, DeQuan [Los Alamos, NM; Jia, Quanxi [Los Alamos, NM
2003-07-08
An organic solvent-free process for deposition of metal oxide thin films is presented. The process includes aqueous solutions of necessary metal precursors and an aqueous solution of a water-soluble polymer. After a coating operation, the resultant coating is fired at high temperatures to yield optical quality metal oxide thin films.
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Aqueous Alkaline Cleaners: An Alternative to Organic Solvents
1993-09-01
F021, F022, F023, F026, F027, F1028) Spent solvents (FOOl, F002, F003, F004, F005) July 8, 1987 California list wastes (Liquid hazardous wastes...installations and has been successful in developing a recycling program to reclaim spent Stoddard solvent and produce a material that meets Army specifications...metal parts it has cleaned. As the contamination level rises, it depletes the solvent’s effective cleaning power until the solvent becomes " spent
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The solvation structures of cellulose microfibrils in ionic liquids.
Mostofian, Barmak; Smith, Jeremy C; Cheng, Xiaolin
2011-12-01
The use of ionic liquids for non-derivatized cellulose dissolution promises an alternative method for the thermochemical pretreatment of biomass that may be more efficient and environmentally acceptable than more conventional techniques in aqueous solution. Here, we performed equilibrium MD simulations of a cellulose microfibril in the ionic liquid 1-butyl-3-methylimidazolium chloride (BmimCl) and compared the solute structure and the solute-solvent interactions at the interface with those from corresponding simulations in water. The results indicate a higher occurrence of solvent-exposed orientations of cellulose surface hydroxymethyl groups in BmimCl than in water. Moreover, spatial and radial distribution functions indicate that hydrophilic surfaces are a preferred site of interaction between cellulose and the ionic liquid. In particular, hydroxymethyl groups on the hydrophilic fiber surface adopt a different conformation from their counterparts oriented towards the fiber's core. Furthermore, the glucose units with these solvent-oriented hydroxymethyls are surrounded by the heterocyclic organic cation in a preferred parallel orientation, suggesting a direct and distinct interaction scheme between cellulose and BmimCl.
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Ikehata, Jun-Ichi; Shinomiya, Kazufusa; Kobayashi, Koji; Ohshima, Hisashi; Kitanaka, Susumu; Ito, Yoichiro
2004-02-06
The effect of Coriolis force on the counter-current chromatographic separation was studied using centrifugal partition chromatography (CPC) with four different two-phase solvent systems including n-hexane-acetonitrile (ACN); tert-butyl methyl ether (MtBE)-aqueous 0.1% trifluoroacetic acid (TFA) (1:1); MtBE-ACN-aqueous 0.1% TFA (2:2:3); and 12.5% (w/w) polyethylene glycol (PEG) 1000-12.5% (w/w) dibasic potassium phosphate. Each separation was performed by eluting either the upper phase in the ascending mode or the lower phase in the descending mode, each in clockwise (CW) and counterclockwise column rotation. Better partition efficiencies were attained by the CW rotation in both mobile phases in all the two-phase solvent systems examined. The mathematical analysis also revealed the Coriolis force works favorably under the CW column rotation for both mobile phases. The overall results demonstrated that the Coriolis force produces substantial effects on CPC separation in both organic-aqueous and aqueous-aqueous two-phase systems.
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Method for recovering and using lignin in adhesive resins by extracting demethylated lignin
Schroeder, Herbert A.
1991-01-01
Lignin, or a lignin derived material, which has been significantly demethylated (e.g., the demethylated lignin found in the raffinate produced as a by-product of dimethyl sulfide production which can be carried out using the spent liquor from wood pulping operations) can be isolated by a process wherein an organic solvent is added to a lignin-containing aqueous solution. The organic solvent is typically a polar, and at least a partially water-immiscible substance such as, for example, ethyl acetate. The resulting lignin-containing aqueous solution/organic solvent mixture is acidified to produce a water layer which is discarded and an organic solvent layer which contains the demethylated lignin. Upon its recovery, the demethylated lignin is preferably dried and stored until it is used (along with an alkali, an aldehyde and an adhesive filler) in compounding an adhesive of the type generally used in the manufacture of plywood.
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Rodil, Rosario; Schellin, Manuela; Popp, Peter
2007-09-07
Membrane-assisted solvent extraction (MASE) in combination with large volume injection-gas chromatography-mass spectrometry (LVI-GC-MS) was applied for the determination of 16 polycyclic aromatic hydrocarbons (PAHs) in aqueous samples. The MASE conditions were optimized for achieving high enrichment of the analytes from aqueous samples, in terms of extraction conditions (shaking speed, extraction temperature and time), extraction solvent and composition (ionic strength, sample pH and presence of organic solvent). Parameters like linearity and reproducibility of the procedure were determined. The extraction efficiency was above 65% for all the analytes and the relative standard deviation (RSD) for five consecutive extractions ranged from 6 to 18%. At optimized conditions detection limits at the ng/L level were achieved. The effectiveness of the method was tested by analyzing real samples, such as river water, apple juice, red wine and milk.
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Structure and dynamics of phosphate ion in aqueous solution: an ab initio QMCF MD study.
Pribil, Andreas B; Hofer, Thomas S; Randolf, Bernhard R; Rode, Bernd M
2008-11-15
A simulation of phosphate in aqueous solution was carried out employing the new QMCF MD approach which offers the possibility to investigate composite systems with the accuracy of a QMMM method but without the time consuming creation of solute-solvent potential functions. The data of the simulations give a clear picture of the hydration shells of the phosphate anion. The first shell consists of 13 water molecules and each oxygen of the phosphate forms in average three hydrogens bonds to different solvent molecules. Several structural parameters such as radial distribution functions and coordination number distributions allow to fully characterize the embedding of the highly charged phosphate ion in the solvent water. The dynamics of the hydration structure of phosphate are described by mean residence times of the solvent molecules in the first hydration shell and the water exchange rate. 2008 Wiley Periodicals, Inc.
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Wet spinning PAN-fibres from aqueous solutions of ZnCl2 and NaSCN
NASA Astrophysics Data System (ADS)
Köhler, T.; Peterek, S.; Gries, T.
2017-10-01
In 2007 a chemical regulation order was adopted in Europe and China, to protect the environment and human beings from hazardous substances in consumer goods and their working environment. It is a topic of interest for the rest of the world, as well. Some substances are banned by law from industrial application. The organic solvents Dimethylformamide (DMF) and Dimethylacetamide (DMAc) are candidates for prohibition. To be prepared, the producers of carbon fibres, hollow fibres and wet spun textile products are looking for alternative solvents for their production processes and try to gain according process Know- How. Aqueous solutions of inorganic salts are the most promising alternative. Within this work, the the major differences between the organic and inorganic solvents are shown and the effects on the production costs are shown. This should show the chances which are linked with the use of the alternative solvents.
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Method for recovering and using lignin in adhesive resins by extracting demethylated lignin
Schroeder, Herbert A.
1991-01-01
Lignin, or a lignin derived material, which has been significantly demethylated (e.g., the demethylated lignin found in the raffinate produced as a by-product of dimethyl sulfide production which can be carried out using the spent liquor from wood pulping operations) can be isolated by a process wherein an organic solvent is added to a lignin-containing aqueous solution. The organic solvent is typically a polar, and at least a partially water-immiscible substance such as, for example, ethyl acetate. The resulting lignin-containing aqueous solution/organic solvent mixture is acidified to produce a water layer which is discarded and an organic solvent layer which contains the demethylated lignin. Upon its recovery, the demethylated lignin is dissolved in an alkaline solution to which an aldehyde source is added to produce a resol-type resin. The aldehyde source may be formaldehyde in solution, paraformaldehyde, hexamethylenetetramine, or other aldehydes including acetaldehyde, furfural, and their derivatives.
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Method for recovering and using lignin in adhesive resins
Schroeder, Herbert A.
1993-01-01
Lignin, or a lignin derived material, which has been significantly demethylated (e.g., the demethylated lignin found in the raffinate produced as a by-product of dimethyl sulfide production which can be carried out using the spent liquor from wood pulping operations) can be isolated by a process wherein an organic solvent is added to a lignin-containing aqueous solution. The organic solvent is typically a polar, and at least a partially water-immiscible substance such as, for example, ethyl acetate. The resulting lignin-containing aqueous solution/organic solvent mixture is acidified to produce a water layer which is discarded and an organic solvent layer which contains the demethylated lignin. Upon its recovery, the demethylated lignin is dissolved in an alkaline solution to which an aldehyde source is added to produce a resol-type resin. The aldehyde source may be formaldehyde in solution, paraformaldehyde, hexamethylenetetramine, or other aldehydes including acetaldehyde, furfural, and their derivatives.
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Separation of chemical groups from bio-oil aqueous phase via sequential organic solvent extraction
DOE Office of Scientific and Technical Information (OSTI.GOV)
Ren, Shoujie; Ye, Philip; Borole, Abhijeet P
Bio-oil aqueous phase contains a considerable amount of furans, alcohols, ketones, aldehydes and phenolics besides the major components of organic acids and anhydrosugars. The complexity of bio-oil aqueous phase limits its efficient utilization. To improve the efficiency of bio-oil biorefinery, this study focused on the separation of chemical groups from bio-oil aqueous phase via sequential organic solvent extractions. Due to their high recoverability and low solubility in water, four solvents (hexane, petroleum ether, chloroform, and ethyl acetate) with different polarities were evaluated, and the optimum process conditions for chemical extraction were determined. Chloroform had high extraction efficiency for furans, phenolics,more » and ketones. In addition to these chemical groups, ethyl acetate had high extraction efficiency for organic acids. The sequential extraction by using chloroform followed by ethyl acetate rendered that 62.2 wt.% of original furans, ketones, alcohols, and phenolics were extracted to chloroform, over 62 wt.% acetic acid was extracted to ethyl acetate, resulting in a high concentration of levoglucosan (~53.0 wt.%) in the final aqueous phase. Chemicals separated via the sequential extraction could be used as feedstocks in biorefinery using processes such as catalytic upgrading of furans and phenolics to hydrocarbons, fermentation of levoglucosan to produce alcohols and diols, and hydrogen production from organic acids via microbial electrolysis.« less
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Separation of chemical groups from bio-oil aqueous phase via sequential organic solvent extraction
Ren, Shoujie; Ye, Philip; Borole, Abhijeet P
2017-01-05
Bio-oil aqueous phase contains a considerable amount of furans, alcohols, ketones, aldehydes and phenolics besides the major components of organic acids and anhydrosugars. The complexity of bio-oil aqueous phase limits its efficient utilization. To improve the efficiency of bio-oil biorefinery, this study focused on the separation of chemical groups from bio-oil aqueous phase via sequential organic solvent extractions. Due to their high recoverability and low solubility in water, four solvents (hexane, petroleum ether, chloroform, and ethyl acetate) with different polarities were evaluated, and the optimum process conditions for chemical extraction were determined. Chloroform had high extraction efficiency for furans, phenolics,more » and ketones. In addition to these chemical groups, ethyl acetate had high extraction efficiency for organic acids. The sequential extraction by using chloroform followed by ethyl acetate rendered that 62.2 wt.% of original furans, ketones, alcohols, and phenolics were extracted to chloroform, over 62 wt.% acetic acid was extracted to ethyl acetate, resulting in a high concentration of levoglucosan (~53.0 wt.%) in the final aqueous phase. Chemicals separated via the sequential extraction could be used as feedstocks in biorefinery using processes such as catalytic upgrading of furans and phenolics to hydrocarbons, fermentation of levoglucosan to produce alcohols and diols, and hydrogen production from organic acids via microbial electrolysis.« less
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SOLVENT EXTRACTION OF URANIUM VALUES
Feder, H.M.; Ader, M.; Ross, L.E.
1959-02-01
A process is presented for extracting uranium salt from aqueous acidic solutions by organic solvent extraction. It consists in contacting the uranium bearing solution with a water immiscible dialkylacetamide having at least 8 carbon atoms in the molecule. Mentioned as a preferred extractant is dibutylacetamide. The organic solvent is usually used with a diluent such as kerosene or CCl/sub 4/.
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Yan, Hongyuan; Yang, Chen; Sun, Yunyun; Row, Kyung Ho
2014-09-26
A new type of ionic liquid molecularly imprinted polymers (IL-MIPs) synthesized by precipitation polymerization using 1-allyl-3-methylimidazolium bromide as an auxiliary solvent and α-chloro-dichlorodiphenyltrichloroethane (α-chloro-DDT) as the template was applied as a selective sorbent of minimized pipette tip-solid-phase extraction (PT-SPE) for rapid isolation and extraction of dicofol (DCF) from celery samples. The pretreatment procedure of celery samples involved only 2.0mg of IL-MIPs, 0.8 mL of acetonitrile-water (ACN-H2O; 1:1, v/v) (washing solvent), and 1.0 mL of acetone-10% acetic acid (HOAc) (elution solvent). Compared with molecularly imprinted polymers (MIPs), ionic liquid-non-imprinted polymers (IL-NIPs) and conventional sorbents such as C18, Si, NH2, and Al2O3-N, IL-MIPs showed higher adsorption and purification capacity to DCF in aqueous solution. Good linearity for DCF was observed in the range from 2.3 to 232.5 ng g(-1) (r(2)=0.9995). The average recoveries at three spiking levels ranged from 86.6% to 101.9% with relative standard deviations (RSDs) of ≤ 6.5% (n=3). The presented IL-MIPs-PT-SPE-GC/ECD method combines the advantages of MIPs, IL, and PT-SPE, and can be used in aqueous conditions with high affinity and selectivity to analytes of complex samples. Copyright © 2014 Elsevier B.V. All rights reserved.
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Aqueous-based thick photoresist removal for bumping applications
NASA Astrophysics Data System (ADS)
Moore, John C.; Brewer, Alex J.; Law, Alman; Pettit, Jared M.
2015-03-01
Cleaning processes account for over 25% of processing in microelectronic manufacturing [1], suggesting electronics to be one of the most chemical intensive markets in commerce. Industry roadmaps exist to reduce chemical exposure, usage, and waste [2]. Companies are encouraged to create a safer working environment, or green factory, and ultimately become certified similar to LEED in the building industry [3]. A significant step in this direction is the integration of aqueous-based photoresist (PR) strippers which eliminate regulatory risks and cut costs by over 50%. One of the largest organic solvent usages is based upon thick PR removal during bumping processes [4-6]. Using market projections and the benefits of recycling, it is estimated that over 1,000 metric tons (mt) of residuals originating from bumping processes are incinerated or sent to a landfill. Aqueous-based stripping would eliminate this disposal while also reducing the daily risks to workers and added permitting costs. Positive-tone PR dissolves in aqueous strippers while negative-tone systems are lifted-off from the substrate, bumps, pillars, and redistribution layers (RDL). While the wafers are further processed and rinsed, the lifted-off PR is pumped from the tank, collected onto a filter, and periodically back-flushed to the trash. The PR solids become a non-hazardous plastic waste while the liquids are mixed with the developer stream, neutralized, filtered, and in most cases, disposed to the sewer. Regardless of PR thickness, removal processes may be tuned to perform in <15min, performing at rates nearly 10X faster than solvents with higher bath lives. A balanced formula is safe for metals, dielectrics, and may be customized to any fab.
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Low-Cost Aqueous Coal Desulfurization
NASA Technical Reports Server (NTRS)
Kalvinskas, J. J.; Vasilakos, N.; Corcoran, W. H.; Grohmann, K.; Rohatgi, N. K.
1982-01-01
Water-based process for desulfurizing coal not only eliminates need for costly organic solvent but removes sulfur more effectively than an earlier solvent-based process. New process could provide low-cost commercial method for converting high-sulfur coal into environmentally acceptable fuel.
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SEPARATION OF SCANDIUM VALUES FORM IRON VALUES BY SOLVENT EXTRACTION
Kuhlman, C.W. Jr.; Lang, G.P.
1961-12-19
A process is given for separating scandium from trivalent iron values. In this process, an aqueous nitric acid solution is contacted with a water- immiscible alkyl phosphate solution, the aqueous solution containing the values to be separated, whereby the scandium is taken up by the alkyl phosphate. The aqueous so1ution is preferably saturated with magnesium nitrate to retain the iron in the aqueous solution. (AEC)
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Halogen-bonding-triggered supramolecular gel formation
NASA Astrophysics Data System (ADS)
Meazza, Lorenzo; Foster, Jonathan A.; Fucke, Katharina; Metrangolo, Pierangelo; Resnati, Giuseppe; Steed, Jonathan W.
2013-01-01
Supramolecular gels are topical soft materials involving the reversible formation of fibrous aggregates using non-covalent interactions. There is significant interest in controlling the properties of such materials by the formation of multicomponent systems, which exhibit non-additive properties emerging from interaction of the components. The use of hydrogen bonding to assemble supramolecular gels in organic solvents is well established. In contrast, the use of halogen bonding to trigger supramolecular gel formation in a two-component gel (‘co-gel’) is essentially unexplored, and forms the basis for this study. Here, we show that halogen bonding between a pyridyl substituent in a bis(pyridyl urea) and 1,4-diiodotetrafluorobenzene brings about gelation, even in polar media such as aqueous methanol and aqueous dimethylsulfoxide. This demonstrates that halogen bonding is sufficiently strong to interfere with competing gel-inhibitory interactions and create a ‘tipping point’ in gel assembly. Using this concept, we have prepared a halogen bond donor bis(urea) gelator that forms co-gels with halogen bond acceptors.
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Angelis, Apostolis; Urbain, Aurélie; Halabalaki, Maria; Aligiannis, Nektarios; Skaltsounis, Alexios-Leandros
2011-09-01
The value-added γ-oryzanol was purified in one step from crude rice bran oil (RBO) using a preparative hydrostatic countercurrent chromatography (hydrostatic CCC) method, operating in the dual mode. The fractionation was performed using a non-aqueous biphasic solvent system consisting of heptane-acetonitrile-butanol (1.8:1.4:0.7, v/v/v), leading rapidly to the target compounds. Transfer of the analytical CCC method to large-scale isolation was also carried out yielding a high quantity-high purity fraction of γ-oryzanol. In addition, a fraction of hydroxylated triterpene alcohol ferulates (polar γ-oryzanol) was clearly separated and obtained. Furthermore, a fast HPLC-APCI(±)-HRMS method was developed and applied for the identification of γ-oryzanol as well as the polar γ-oryzanol in RBO and the resulting fractions. The purity of γ-oryzanol fraction was estimated as 97% based on HPLC-APCI-HRMS analysis. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Non-aqueous electrolyte for lithium-ion battery
Amine, Khalil; Zhang, Lu; Zhang, Zhengcheng
2016-01-26
A substantially non-aqueous electrolyte solution includes an alkali metal salt, a polar aprotic solvent, and an organophosphorus compound of Formula IA, IB, or IC: ##STR00001## where R.sup.1, R.sup.2, R.sup.3 and R.sup.4 are each independently hydrogen, halogen, alkyl, alkenyl, alkynyl, cycloalkyl, aryl, heterocyclyl, heteroaryl, alkoxy, alkenoxy, alkynoxy, cycloalkoxy, aryloxy, heterocyclyloxy, heteroaryloxy, siloxyl, silyl, or organophosphatyl; R.sup.5 and R.sup.6 are each independently alkyl, alkenyl, alkynyl, cycloalkyl, aryl, heterocyclyl, or heteroaryl; R.sup.7 is ##STR00002## and R.sup.8, R.sup.9 and R.sup.10 are each independently alkyl, cycloalkyl, aryl, heterocyclyl, or heteroaryl; provided that if the organophosphorus compound is of Formula IB, then at least one of R.sup.5, and R.sup.6 are other than hydrogen, alkyl, or alkenyl; and if the organophosphorus compound is of Formula IC, then the electrolyte solution does not include 4-methylene-1,3-dioxolan-2-one or 4,5-dimethylene-1,3-dioxolan-2-one.
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[Extraction of lambda-cyhalothrin from aqueous dioxan solutions].
Shormanov, V K; Chigareva, E N; Belousova, O V
2011-01-01
The results of extraction of lambda-cigalotrin from dioxan aqueous solutions by hydrophobic organic solvents are presented. It is shown that the degree of extraction depends on the nature of the extractant, the water to dioxan ratio, and saturation of the water-dioxan layer with the electrolyte. The highest efficiency of lambda-cigalotrin extraction was achieved using chlorophorm as a solvent under desalination conditions. The extraction factor was calculated necessary to obtain the desired amount of lambda-cigalotrin from the water-dioxan solution (4:1) with the help of the extractants being used.
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NASA Astrophysics Data System (ADS)
Burov, D. M.; Ledenkov, S. F.; Vandyshev, V. N.
2013-05-01
Constants of the acid dissociation and complexation of L-phenylalanine (HPhe) with copper(II) ions are determined by potentiometry in aqueous ethanol solutions containing 0 to 0.7 molar fraction of alcohol. Changes in the Gibbs energy for the transfer from water to a binary solvent of L-phenylalanine, Phe- anion, and [CuPhe]+ complex are calculated. It is found that the weakening of solvation of the ligand donor groups in solvents with high ethanol contents is accompanied by an increase in the stability of [CuPhe]+ complex.
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NASA Astrophysics Data System (ADS)
Sharma, Poonam; Chauhan, S.; Syal, V. K.; Chauhan, M. S.
2008-04-01
Partial molar volumes of the drugs Parvon Spas, Parvon Forte, Tramacip, and Parvodex in aqueous mixtures of methanol (MeOH), ethanol (EtOH), and propan-1-ol (1-PrOH) have been determined. The data have been evaluated using the Masson equation. The parameters, apparent molar volumes {(φ_v)}, partial molar volumes {(φ_v0)}, and S v values (experimental slopes) have been interpreted in terms of solute solvent interactions. In addition, these studies have also been extended to determine the effect of these drugs on the solvation behavior of an electrolyte (sodium chloride), a surfactant (sodium dodecyl sulfate), and a non-electrolyte (sucrose). It can be inferred from these studies that all drug cations can be regarded as structure makers/promoters due to hydrophobic hydration. Furthermore, the results are correlated to understand the solution behavior of drugs in aqueous-alcoholic systems, as a function of the nature of the alcohol and solutes.
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Effect of solvent polarity on the extraction of components of pharmaceutical plastic containers.
Ahmad, Iqbal; Sabah, Arif; Anwar, Zubair; Arif, Aysha; Arsalan, Adeel; Qadeer, Kiran
2017-01-01
A study of the extraction of polymeric material and dyes from the pharmaceutical plastic containers using various organic solvents was conducted to evaluate the effect of polarity on the extraction process. The plastic containers used included semi-opaque, opaque, transparent and amber colored and the solvent used were acetonitrile, methanol, ethanol, acetone, dichloroethane, chloroform and water. The determination of extractable material was carried out by gravimetric and spectrometric methods. The yield of extractable materials from containers in 60 h was 0.10-1.29% (w/w) and the first-order rate constant (kobs) for the extraction of polymeric material ranged from 0.52-1.50 × 10-3 min -1 and for the dyes 6.43- 6.74 x10-3min-1. The values of (k obs ) were found to be an inverse function of solvent dielectric constant and decreased linearly with the solvent acceptor number. The extractable polymeric materials exhibited absorption in the 200-400 nm region and the dyes in the 300-500nm region. The rates of extraction of polymeric material and dyes from plastic containers were dependent on the solvent dielectric constant. The solvents of low polarity were more effective in the extraction of material indicating that the extracted material were of low polarity or have non-polar character. The dyes were soluble in acetone and chloroform. No plastic material was found to be extracted from the containers in aqueous solution.
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Method for cleaning and passivating a metal surface
NASA Technical Reports Server (NTRS)
Alexander, George B. (Inventor); Carpenter, Norman F. (Inventor)
1976-01-01
A cleaning solvent useful in the cleaning of metal surfaces, e.g. nickle-iron alloys, contains sulfamic acid, citric acid, a solvent for hydrocarbon residues, and a surfactant. Metal surfaces are cleaned by contacting the surface with the cleaning solvent and then passivated by contact with aqueous solutions of citric acid or sodium nitrite or a combination of the two.
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Felmy, Heather M.; Bennett, Kevin T.; Clark, Sue B.
2017-05-12
To gain insight on the role of mixed solvents on the thermodynamic driving forces for the complexation between trivalent f-elements and organic ligands, solution phase thermodynamic parameters were determined for Eu(III) complexation with 2-hydroxyisobutyric acid (HIBA) and 2-aminoisobutyric acid (AIBA) in mixed methanol (MeOH)-water and N,N-dimethylformamide (DMF)-water solvents. Included in this study were the determination of mixed solvent autoprotolysis constants (pK α) as well as the thermodynamic formation constants: log β, ΔG, ΔH, and ΔS, for ligand protonation and Eu(III)-ligand complexation utilizing potentiometry and calorimetry techniques. The results presented are conditional thermodynamic values determined at an ionic strength of 1.0more » M NaClO 4 and a temperature of 298 K. It was found that moving from an aqueous solution to a binary aqueous-organic solvent affected all solution equilibria to some degree and that the extent of change depended on both the type of mixed solvent and the ligand in each study. Here, the ability to understand and predict these changes in thermodynamic values as a function of solvent composition provides important information about the chemistry of the trivalent f-elements.« less
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Felmy, Heather M.; Bennett, Kevin T.; Clark, Sue B.
To gain insight on the role of mixed solvents on the thermodynamic driving forces for the complexation between trivalent f-elements and organic ligands, solution phase thermodynamic parameters were determined for Eu(III) complexation with 2-hydroxyisobutyric acid (HIBA) and 2-aminoisobutyric acid (AIBA) in mixed methanol (MeOH)-water and N,N-dimethylformamide (DMF)-water solvents. Included in this study were the determination of mixed solvent autoprotolysis constants (pK α) as well as the thermodynamic formation constants: log β, ΔG, ΔH, and ΔS, for ligand protonation and Eu(III)-ligand complexation utilizing potentiometry and calorimetry techniques. The results presented are conditional thermodynamic values determined at an ionic strength of 1.0more » M NaClO 4 and a temperature of 298 K. It was found that moving from an aqueous solution to a binary aqueous-organic solvent affected all solution equilibria to some degree and that the extent of change depended on both the type of mixed solvent and the ligand in each study. Here, the ability to understand and predict these changes in thermodynamic values as a function of solvent composition provides important information about the chemistry of the trivalent f-elements.« less
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EVALUATION OF ALTERNATIVES TO CHLORINATED SOLVENTS FOR METAL CLEANING
This project report details results of investigations into alternatives to chlorinated solvents used for metal degreasing. Three companies participated in this project. The results reported for one company document a situation where the conversion to an aqueous cleaning system ha...
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Kler, Pablo A; Huhn, Carolin
2014-11-01
Isotachophoresis (ITP) has long been used alone but also as a preconcentration technique for capillary electrophoresis (CE). Unfortunately, up to now, its application is restricted to relatively strong acids and bases as either the degree of (de)protonation is too low or the water dissociation is too high, evoking zone electrophoresis. With the comprehensive ITP analysis of all 20 proteinogenic amino acids as model analytes, we, here, show that non-aqueous ITP using dimethylsulfoxide as a solvent solves this ITP shortcoming. Dimethylsulfoxide changes the pH regime of analytes and electrolytes but, more importantly, strongly reduces the proton mobility by prohibiting hydrogen bonds and thus, the so-called Zundel-Eigen-Zundel electrical conduction mechanism of flipping hydrogen bonds. The effects are demonstrated in an electrolyte system with taurine or H(+) as terminator, and imidazole as leader together with strong acids such as oxalic and even trifluoroacetic acid as counterions, both impossible to use in aqueous solution. Mass spectrometric as well as capacitively coupled contactless conductivity detection (C(4)D) are used to follow the ITP processes. To demonstrate the preconcentration capabilities of ITP in a two-dimensional set-up, we, here, also demonstrate that our non-aqueous ITP method can be combined with capillary electrophoresis-mass spectrometry in a column-coupling system using a hybrid approach of capillaries coupled to a microfluidic interface. For this, C(4)D was optimized for on-chip detection with the electrodes aligned on top of a thin glass lid of the microfluidic chip.
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Liu, Dan; Zou, Xiaowei; Gao, Mingzhe; Gu, Ming; Xiao, Hongbin
2014-08-22
Hydrophilic organic/salt-containing aqueous two-phase system composing of ethanol, water and ammonium sulfate for separation polar compounds was investigated on multilayer coil associated with J-type HSCCC devices. Compared to the classical polar solvent system based on 1-butanol-water or PEG1000-ammonium sulfate-water, the water content of upper phase in ethanol-ammonium sulfate-water systems was from 53.7% to 32.8% (wt%), closed to PEG1000-ammonium sulfate-water aqueous two-phase systems and higher than 1-butanol-water (22.0%, wt%). Therefore, the polarity of ethanol-ammonium sulfate-water is in the middle of 1-butanol-water and PEG-ammonium sulfate-water system, which is quite good for separating polar compounds like phenols, nucleosides and amino acids with low partition coefficient in 1-octanol-water system. The retention of stationary phase in four elution mode on type-J counter-current chromatography devices with multilayer coil column changed from 26% to 71%. Hydrodynamic trend possess both intermediate and hydrophilic solvent system property, which closely related to the composition of solvent system. The applicability of this system was demonstrated by successful separation of adenosine, uridine guanosine and cytidine. Copyright © 2014 Elsevier B.V. All rights reserved.
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Barzagli, Francesco; Mani, Fabrizio; Peruzzini, Maurizio
2016-07-05
The neat secondary amines 2-(methylamino)ethanol, 2-(ethylamino)ethanol, 2-(isopropylamino)ethanol, 2-(benzylamino)ethanol and 2-(butylamino)ethanol react with CO2 at 50-60 °C and room pressure yielding liquid carbonated species without their dilution with any additional solvent. These single-component absorbents have the theoretical CO2 capture capacity of 0.50 (mol CO2/mol amine) due to the formation of the corresponding amine carbamates and protonated amines that were identified by the (13)C NMR analysis. These single-component absorbents were used for CO2 capture (15% and 40% v/v in air) in two series of different procedures: (1) batch experiments aimed at investigating the efficiency and the rate of CO2 capture; (2) continuous cycles of absorption-desorption carried out in packed columns with absorption temperatures brought at 50-60 °C and desorption temperatures at 100-120 °C at room pressure. A number of different amines and experimental setups gave CO2 capture efficiency greater than 90%. For comparison purposes, 30 wt % aqueous MEA was used for CO2 capture under the same operational conditions described for the solvent-free amines. The potential advantages of solvent-free alkanolamines over aqueous MEA in the CO2 capture process were discussed.
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Lipase in aqueous-polar organic solvents: Activity, structure, and stability
Kamal, Md Zahid; Yedavalli, Poornima; Deshmukh, Mandar V; Rao, Nalam Madhusudhana
2013-01-01
Studying alterations in biophysical and biochemical behavior of enzymes in the presence of organic solvents and the underlying cause(s) has important implications in biotechnology. We investigated the effects of aqueous solutions of polar organic solvents on ester hydrolytic activity, structure and stability of a lipase. Relative activity of the lipase monotonically decreased with increasing concentration of acetone, acetonitrile, and DMF but increased at lower concentrations (upto ∼20% v/v) of dimethylsulfoxide, isopropanol, and methanol. None of the organic solvents caused any appreciable structural change as evident from circular dichorism and NMR studies, thus do not support any significant role of enzyme denaturation in activity change. Change in 2D [15N, 1H]-HSQC chemical shifts suggested that all the organic solvents preferentially localize to a hydrophobic patch in the active-site vicinity and no chemical shift perturbation was observed for residues present in protein's core. This suggests that activity alteration might be directly linked to change in active site environment only. All organic solvents decreased the apparent binding of substrate to the enzyme (increased Km); however significantly enhanced the kcat. Melting temperature (Tm) of lipase, measured by circular dichroism and differential scanning calorimetry, altered in all solvents, albeit to a variable extent. Interestingly, although the effect of all organic solvents on various properties on lipase is qualitatively similar, our study suggest that magnitudes of effects do not appear to follow bulk solvent properties like polarity and the solvent effects are apparently dictated by specific and local interactions of solvent molecule(s) with the protein. PMID:23625694
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Improvement of activity and stability of chloroperoxidase by chemical modification
Liu, Jian-Zhong; Wang, Min
2007-01-01
Background Enzymes show relative instability in solvents or at elevated temperature and lower activity in organic solvent than in water. These limit the industrial applications of enzymes. Results In order to improve the activity and stability of chloroperoxidase, chloroperoxidase was modified by citraconic anhydride, maleic anhydride or phthalic anhydride. The catalytic activities, thermostabilities and organic solvent tolerances of native and modified enzymes were compared. In aqueous buffer, modified chloroperoxidases showed similar Km values and greater catalytic efficiencies kcat/Km for both sulfoxidation and oxidation of phenol compared to native chloroperoxidase. Of these modified chloroperoxidases, citraconic anhydride-modified chloroperoxidase showed the greatest catalytic efficiency in aqueous buffer. These modifications of chloroperoxidase increased their catalytic efficiencies for sulfoxidation by 12%~26% and catalytic efficiencies for phenol oxidation by 7%~53% in aqueous buffer. However, in organic solvent (DMF), modified chloroperoxidases had lower Km values and higher catalytic efficiencies kcat/Km than native chloroperoxidase. These modifications also improved their thermostabilities by 1~2-fold and solvent tolerances of DMF. CD studies show that these modifications did not change the secondary structure of chloroperoxidase. Fluorescence spectra proved that these modifications changed the environment of tryptophan. Conclusion Chemical modification of epsilon-amino groups of lysine residues of chloroperoxidase using citraconic anhydride, maleic anhydride or phthalic anhydride is a simple and powerful method to enhance catalytic properties of enzyme. The improvements of the activity and stability of chloroperoxidase are related to side chain reorientations of aromatics upon both modifications. PMID:17511866
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Solventless pharmaceutical coating processes: a review.
Bose, Sagarika; Bogner, Robin H
2007-01-01
Coatings are an essential part in the formulation of pharmaceutical dosage form to achieve superior aesthetic quality (e.g., color, texture, mouth feel, and taste masking), physical and chemical protection for the drugs in the dosage forms, and modification of drug release characteristics. Most film coatings are applied as aqueous- or organic-based polymer solutions. Both organic and aqueous film coating bring their own disadvantages. Solventless coating technologies can overcome many of the disadvantages associated with the use of solvents (e.g., solvent exposure, solvent disposal, and residual solvent in product) in pharmaceutical coating. Solventless processing reduces the overall cost by eliminating the tedious and expensive processes of solvent disposal/treatment. In addition, it can significantly reduce the processing time because there is no drying/evaporation step. These environment-friendly processes are performed without any heat in most cases (except hot-melt coating) and thus can provide an alternative technology to coat temperature-sensitive drugs. This review discusses and compares six solventless coating methods - compression coating, hot-melt coating, supercritical fluid spray coating, electrostatic coating, dry powder coating, and photocurable coating - that can be used to coat the pharmaceutical dosage forms.
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Molina, M Jesús; Gómez-Antón, M Rosa; Piérola, Inés F
2007-10-25
The number of variables controlling the behavior of ionic gels is large and very often some of them are unknown. The aim of this work is to interpret quantitatively the swelling behavior of pH sensitive gels, with the minimum number of simplifying assumptions. With this purpose, the equilibrium degree of swelling (S) and protonation (alpha) of chemically cross-linked poly(N-vinylimidazole) (PVI) immersed in aqueous salt solutions were measured as a function of the ionic strength (mu), in the whole range of pH. In acid solutions with pH in the range 0 to 4, imidazole moieties become protonated, and PVI behaves as a polyelectrolyte gel: S decreases upon increasing mu both for NaCl and for CaCl(2), with HCl as protonating acid. In aqueous solutions with larger pH, between 4 and 12, the hydrogel is practically neutral, and S increases as mu rises, showing a salting-in effect. From the quantitative analysis of these results, the following facts emerged. Protonation induces chain stiffness (as measured by the non-Gaussian factor) and worsening of the solvent quality of the aqueous media (as measured by the polymer-solvent interaction parameter). For alpha below 33%, swelling seems to be governed by the excess of mobile counterions inside the gel with respect to the bath, with a minor but still significantly negative contribution of the osmotic swelling pressure due to polymer-solvent mixing. Above 33% protonation, it is necessary to consider Manning counterion condensation to get parameters with physical meaning. The crossover between polyelectrolyte and salting-in effects corresponds to alpha and mu values with the same ionic and mixing contributions to the osmotic swelling pressure. The formation of ionic nonpermanent cross-links, with H(2)SO(4) as the protonating acid, was discarded.
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SLURRY SOLVENT EXTRACTION PROCESS FOR THE RECOVERY OF METALS FROM SOLID MATERIALS
Grinstead, R.R.
1959-01-20
A solvent extraction process is described for recovering uranium from low grade uranium bearing minerals such as carnotit or shale. The finely communited ore is made up as an aqueous slurry containing the necessary amount of acid to solubilize the uranium and simultaneously or subsequently contacted with an organic solvent extractant such as the alkyl ortho-, or pyro phosphoric acids, alkyl phosphites or alkyl phosphonates in combination with a diluent such as kerosene or carbon tetrachlorids. The extractant phase is separated from the slurry and treated by any suitable process to recover the uranium therefrom. One method for recovering the uranium comprises treating the extract with aqueous HF containing a reducing agent such as ferrous sulfate, which reduces the uranium and causes it to be precipitated as uranium tetrafluoride.
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This technology utilizes liquified gases as the extracting solvent to remove organics, such as hydrocarbons, oil and grease, from wastewater or contaminated sludges and soils. Carbon dioxide is generally used for aqueous solutions, and propane is used for sediment, sludges and ...
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A novel TFC forward osmosis (FO) membrane supported by polyimide (PI) microporous nanofiber membrane
NASA Astrophysics Data System (ADS)
Chi, Xiang-Yu; Zhang, Ping-Yun; Guo, Xue-Jiao; Xu, Zhen-Liang
2018-01-01
A novel interfacial polymerization (IP) procedure on polyimide (PI) microporous nanofiber membrane support with mean pore size 1.27 μm was reported. Using m-phenylenediamine (MPD) as aqueous phase monomer, trimesoyl chloride (TMC) as organic phase monomer, ethanol as aqueous phase co-solvent, thin-film composite (TFC) forward osmosis (FO) membrane was fabricated by two IP procedures. The first IP procedure with the unconventional order (ie, the membrane was immersed in the TMC organic phase first, then in the co-solvent ethanol-water MPD aqueous phase) was used to diminish the pore size of PI microporous nanofiber membrane support for the formation of the polyamide layer. The secondary IP procedure was employed to form the relatively dense polyamide layer with conventional order (ie, the membrane was immersed in the co-solvent ethanol-water MPD aqueous phase first, then in the TMC organic phase). The experimental results showed that higher ethanol concentration led to the relatively higher pure water permeability in RO process and osmotic water flux in FO process, whereas NaCl rejection in RO process decreased and reverse salt flux increased. The specific salt flux (Js/Jv) of TFC FO PI nanofiber membrane (PIN-2-4) could be as low as 0.095 g/L in FO mode. These results could be attributed to influence of the addition of ethanol into aqueous phase on the surface morphology, hydrophilicity and polyamide layer structure.
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NASA Astrophysics Data System (ADS)
Gamov, G. A.; Grazhdan, K. V.; Gavrilova, M. A.; Dushina, S. V.; Sharnin, V. A.; Baranski, A.
2013-06-01
Solutions of iron(III) perchlorate in water, water-ethanol, and water-dimethyl sulfoxide solvents (x_{H_2 O} = 0.7 and 0.25 mole fractions) at ionic strength values I = 0.1, 0.25, and 0.5 are studied by IR spectroscopy. Analysis of the absorption bands of perchlorate ion shows that it does not participate in association processes. It is demonstrated that in the range of ionic strength values between 0 and 0.5 (NaClO4), it affects neither the results from potentiometric titration to determine the stability constants of the iron(III)-nicotinamide complex nor the thermal effects of complexation determined via direct calorimetry in a binary solvent containing 0.3 mole fractions (m.f.) of a non-aqueous component.
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Ultrafast excited-state deactivation of 9-methylhypoxanthine in aqueous solution: A QM/MM MD study
DOE Office of Scientific and Technical Information (OSTI.GOV)
Guo, Xugeng, E-mail: xgguo@henu.edu.cn, E-mail: zhangjinglai@henu.edu.cn; Yuan, Huijuan; An, Beibei
Photoinduced ultrafast non-adiabatic decay of 9-methylhypoxanthine (9MHPX) in aqueous solution was investigated by ab initio surface-hopping dynamics calculations using a combined quantum mechanical/molecular mechanical approach. The absorption spectra of 9MHPX in aqueous solution were also explored by the hybrid cluster-continuum model at the level of time-dependent density functional theory along with the polarizable continuum model (PCM). The static electronic-structure calculations indicate that the absorption spectra of 9MHPX simulated by TD-B3LYP/PCM and TD-X3LYP/PCM can reproduce very well the experimental findings, with the accuracy of about 0.20 eV. According to dynamics simulations, irradiation of 9MHPX populates the bright excited singlet S{sub 1}more » state, which may undergo an ultrafast non-radiative deactivation to the S{sub 0} state. The lifetime of the S{sub 1} state of 9MHPX in aqueous solution is predicted to be 115.6 fs, slightly longer than that in the gas phase (88.8 fs), suggesting that the solvent water has no significant influence on the excited-state lifetime of 9MHPX. Such a behavior in 9MHPX is distinctly different from its parent hypoxanthine keto-N9H tautomer in which the excited-state lifetime of the latter in water solution was remarkably enhanced as compared to the gas phase. The significant difference of the photodynamical behaviors between 9MHPX and keto-N9H can be ascribed to their different hydrogen bond environment in aqueous solution.« less
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NASA Astrophysics Data System (ADS)
McLafferty, Jason
Chemical storage of hydrogen involves release of hydrogen in a controlled manner from materials in which the hydrogen is covalently bound. Sodium borohydride and aminoborane are two materials given consideration as chemical hydrogen storage materials by the US Department of Energy. A very significant barrier to adoption of these materials as hydrogen carriers is their regeneration from "spent fuel," i.e., the material remaining after discharge of hydrogen. In this thesis, some research directed at regeneration of sodium borohydride and aminoborane is described. For sodium borohydride, electrochemical reduction of boric acid and sodium metaborate (representing spent fuel) in alkaline, aqueous solution has been investigated. Similarly to literature reports (primarily patents), a variety of cathode materials were tried in these experiments. Additionally, approaches directed at overcoming electrostatic repulsion of borate anion from the cathode, not described in the previous literature for electrochemical reduction of spent fuels, have been attempted. A quantitative analytical method for measuring the concentration of sodium borohydride in alkaline aqueous solution has been developed as part of this work and is described herein. Finally, findings from stability tests for sodium borohydride in aqueous solutions of several different compositions are reported. For aminoborane, other research institutes have developed regeneration schemes involving tributyltin hydride. In this thesis, electrochemical reduction experiments attempting to regenerate tributyltin hydride from tributyltin chloride (a representative by-product of the regeneration scheme) are described. These experiments were performed in the non-aqueous solvents acetonitrile and 1,2-dimethoxyethane. A non-aqueous reference electrode for electrolysis experiments in acetonitrile was developed and is described.
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Ovanesyan, Zaven; Fenley, Marcia O.; Guerrero-García, Guillermo Iván; Olvera de la Cruz, Mónica
2014-01-01
The ionic atmosphere around a nucleic acid regulates its stability in aqueous salt solutions. One major source of complexity in biological activities involving nucleic acids arises from the strong influence of the surrounding ions and water molecules on their structural and thermodynamic properties. Here, we implement a classical density functional theory for cylindrical polyelectrolytes embedded in aqueous electrolytes containing explicit (neutral hard sphere) water molecules at experimental solvent concentrations. Our approach allows us to include ion correlations as well as solvent and ion excluded volume effects for studying the structural and thermodynamic properties of highly charged cylindrical polyelectrolytes. Several models of size and charge asymmetric mixtures of aqueous electrolytes at physiological concentrations are studied. Our results are in good agreement with Monte Carlo simulations. Our numerical calculations display significant differences in the ion density profiles for the different aqueous electrolyte models studied. However, similar results regarding the excess number of ions adsorbed to the B-DNA molecule are predicted by our theoretical approach for different aqueous electrolyte models. These findings suggest that ion counting experimental data should not be used alone to validate the performance of aqueous DNA-electrolyte models. PMID:25494770
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Phapale, Daulat; Ghosh, Rajib; Das, Dipanwita
2017-06-05
A new tris-heteroleptic complex [Ru(bpy)(dppz)(OSO)](ClO 4 ), [1](ClO 4 ) (bpy = 2,2'-bipyridine, dppz = dipyrido[3,2-a:2',3'-c]phenazine and OSO = 2-methylsulfinylbenzoate), was synthesized and characterized to control the photochromic Ru-S → Ru-O linkage isomerization. Details isomerization kinetics studied by UV-visible absorption spectroscopy and cyclic voltammetry revealed that efficient photochromic S → O isomerization and thermal O → S reversal take place in solvents like propylene carbonate (PC), methanol, and dichloromethane. Strikingly, photoisomerization of [1](ClO 4 ) is arrested in water although is active in the analogous compound [Ru(bpy) 2 (OSO)](ClO 4 ). Effective excited state deactivation through dark 3 MLCT state involving dppz ligand of [1](ClO 4 ) switches off photochromism in aqueous medium. Interestingly, the photochromism is activated in aqueous solution in the presence of DNA which shields the dppz localized dark state through intercalation. Ultrafast transient absorption spectroscopic measurement sheds light on the differential behavior of photochromism in aqueous and nonaqueous solvents.
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Antibacterial properties of the skin mucus of the freshwater fishes, Rita rita and Channa punctatus.
Kumari, U; Nigam, A K; Mitial, S; Mitial, A K
2011-07-01
The skin mucus of Rita rita and Channa punctatus was investigated to explore the possibilities of its antibacterial properties. Skin mucus was extracted in acidic solvents (0.1% trifluoroacetic acid and 3% acetic acid) and in triple distilled water (aqueous medium). The antibacterial activity of the mucus extracts was analyzed, using disc diffusion method, against five strains of bacteria--the Gram-positive Staphylococcus aureus and Micrococcus luteus; and the Gram negative Escherichia coli, Pseudomonas aeruginosa and Salmonella typhi. In both Rita rita and Channa punctatus, the skin mucus extracted in acidic solvents as well as in aqueous medium show antibacterial activity against Staphylococcus aureus and Micrococcus luteus. Nevertheless, the activity is higher in acidic solvents than that in aqueous medium. The acidic mucus extracts of Rita rita, show antibacterial activity against Salmonella typhi as well. The results suggest that fish skin mucus have bactericidal properties and thus play important role in the protection of fish against the invasion of pathogens. Fish skin mucus could thus be regarded as a potential source of novel antibacterial components.
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Behavior of soluble and immobilized acid phosphatase in hydro-organic media.
Wan, H; Horvath, C
1975-11-20
The hydrolysis of p-nitrophenyl phosphate by wheat germ acid phosphatase (orthophosphoric monoester phosphohydrolase, EC 3.1.3.2) has been investigated in mixtures of aqueous buffers with acetone, dioxane and acetonitrile. The enzyme was either in free solution or immobilized on a pellicular support which consisted of a porous carbonaceous layer on solid glass beads. The highest enzyme activity was obtained in acetone and acetonitrile mixed with citrate buffer over a wide range of organic solvent concentration. In 50% (v/v) acetone both V and Km of the immobilized enzyme were about half of the values in the neat aqueous buffer, but the Ki for inorganic phosphate was unchanged. In 50% (v/v) mixtures of various solvents and citrate buffers of different pH, the enzymic activity was found to depend on the pH of the aqueous buffer component rather than the pH of the hydro-organic mixture as measured with the glass-calomel electrode. The relatively high rates of p-nitrophenol liberation in the presence of glucose even at high organic solvent concentrations suggest that transphosphorylation is facilitated at low water activity.
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Regeneration of an aqueous solution from an acid gas absorption process by matrix stripping
Rochelle, Gary T [Austin, TX; Oyenekan, Babatunde A [Katy, TX
2011-03-08
Carbon dioxide and other acid gases are removed from gaseous streams using aqueous absorption and stripping processes. By replacing the conventional stripper used to regenerate the aqueous solvent and capture the acid gas with a matrix stripping configuration, less energy is consumed. The matrix stripping configuration uses two or more reboiled strippers at different pressures. The rich feed from the absorption equipment is split among the strippers, and partially regenerated solvent from the highest pressure stripper flows to the middle of sequentially lower pressure strippers in a "matrix" pattern. By selecting certain parameters of the matrix stripping configuration such that the total energy required by the strippers to achieve a desired percentage of acid gas removal from the gaseous stream is minimized, further energy savings can be realized.
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Morinaga, Osamu; Uto, Takuhiro; Yuan, Chun-Su; Tanaka, Hiroyuki; Shoyama, Yukihiro
2010-06-01
A new eastern blotting technique has been established for ginsenoside Re (G-Re) contained in American ginseng berry pulp extracts. G-Re in American ginseng berry pulp was extracted using 100% methanol, 100% ethanol, 50% aqueous methanol, and 50% aqueous ethanol. The combined crude extracts were applied onto a polyethersulfone membrane and developed using the methanol-water-acetic acid solvent system (45:55:1 v/v). Separated components were immunostained using anti-G-Re monoclonal antibody. G-Re was first specifically detected and then quantitatively analyzed using NIH Imaging software. We also confirmed that the most suitable solvent was 50% aqueous methanol for extracting G-Re from American ginseng berry pulp. (c) 2009 Elsevier B.V. All rights reserved.
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Ozone Depleting Chemical (ODC) Replacement - Alternative Cleaning Solvents and Lubricants.
1995-02-01
surface. This phenomenon helps to explain why some aqueous based cleaners (such as Daraclean®) can effectively remove fluorinated greases (such as...structurally similar to hydrocarbon oils, waxes, and greases it removes. In some fluorinated greases such as Krytox®, only solvents identically similar to...the contaminant (such as Tribolube®, a fluorinated solvent) effectively dissolves them. Hexane and methanol, being members of different chemical
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Anthracene and pyrene photolysis kinetics in aqueous, organic, and mixed aqueous-organic phases
NASA Astrophysics Data System (ADS)
Grossman, Jarod N.; Stern, Adam P.; Kirich, Makena L.; Kahan, Tara F.
2016-03-01
Condensed phases in the atmosphere, such as cloud droplets and aerosols, often contain both water and organic matter (OM). Reactivity can differ significantly between aqueous and organic phases. We have measured photolysis kinetics of the polycyclic aromatic hydrocarbons (PAHs) anthracene and pyrene in several organic solvents and in water, as well as in miscible and phase-separated aqueous-organic mixtures at atmospherically-relevant wavelengths. Photolysis rate constants generally increased with increasing solvent polarity; photolysis of both PAHs was more than ten times faster in water than in octanol. Local polarity had a much greater effect on PAH photolysis kinetics than changes in PAH absorptivity or singlet oxygen concentrations. Photolysis kinetics in homogeneous aqueous-organic mixtures varied monotonically with2 OM volume fraction. Kinetics in immiscible (phase-separated) solutions were more complex, with different dependences on OM content observed in stagnant and turbulent solutions. Our results suggest that OM could greatly affect the photochemical lifetimes of PAHs in atmospheric condensed phases such as aerosols, even if the OM does not itself absorb photons.
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Separation of Gadolinium (Gd) using Synergic Solvent Mixed Topo-D2EHPA with Extraction Method.
NASA Astrophysics Data System (ADS)
Effendy, N.; Basuki, K. T.; Biyantoro, D.; Perwira, N. K.
2018-04-01
The main problem to obtain Gd with high purity is the similarity of chemical properties and physical properties with the other rare earth elements (REE) such as Y and Dy, it is necessary to do separation by the extraction process. The purpose of this research to determine the best solvent type, amount of solvent, feed and solvent ratio in the Gd extraction process, to determine the rate order and the value of the rate constant of Gd concentration based on experimental data of aqueous phase concentration as a function of time and to know the effect of temperature on the reaction speed constant. This research was conducted on variation of solvent, amount of solvent, feed and solvent ratio in the extraction process of Gd separation, extraction time to determine the order value and the rate constant of Gd concentration in extraction process based on the aqueous phase concentration data as a function of time, to the rate constant of decreasing concentration of Gd. Based on the calculation results, the solvent composition was obtained with the best feed to separate the rare earth elements Gd in the extraction process is 1 : 4 with 15% concentration of TOPO and 10% concentration of D2EHPA. The separation process of Gd using extraction method by solvent TOPO-D2EHPA 2 : 1 comparison is better than single solvent D2EHPA / TOPO because of the synergistic effect. The rate order of separation process of Gd follows order 1. The Arrhenius Gd equation becomes k = 1.46 x 10-7 exp (-6.96 kcal / mol / RT).
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Van Eerdenbrugh, Bernard; Raina, Shweta; Hsieh, Yi-Ling; Augustijns, Patrick; Taylor, Lynne S
2014-04-01
To classify the crystallization behavior of amorphous active pharmaceutical ingredients (API) exposed to aqueous environments. A set of approximately 50 chemically and physically diverse active pharmaceutical ingredients (APIs) was selected for this study. Two experimental setups were employed to characterize the crystallization behavior of the amorphous API in an aqueous environment. For the first approach, precipitation, as evidenced by the development of turbidity, was induced using the solvent shift method, by mixing concentrated API solutions in DMSO with an aqueous buffer in a capillary. Subsequently, crystallization was monitored in situ over time using synchrotron radiation (simultaneous SAXS/WAXS beamline 12-ID-B at the Advanced Photon Source, Argonne National Laboratories, Argonne, IL). In the second approach, amorphous films were prepared by melt quenching; after adding buffer, crystallization was monitored with time using polarized light microscopy. In general, the crystallization behavior of a given compound was similar irrespective of the experimental method employed. However, the crystallization behavior among different compounds varied significantly, ranging from immediate and complete crystallization to no observable crystallization over biorelevant time scales. Comparison of the observed behavior with previous studies of crystallization tendency in non-aqueous environments revealed that the crystallization tendency of individual APIs was somewhat similar regardless of the crystallization environment. API properties, rather than the method by which amorphous materials are generated, tend to dictate crystallization behavior in aqueous media.
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A critical study on efficiency of different materials for fluoride removal from aqueous media
2013-01-01
Fluoride is a persistent and non-biodegradable pollutant that accumulates in soil, plants, wildlife and in human beings. Therefore, knowledge of its removal, using best technique with optimum efficiency is needed. The present survey highlights on efficacy of different materials for the removal of fluoride from water. The most important results of extensive studies on various key factors (pH, agitation time, initial fluoride concentration, temperature, particle size, surface area, presence and nature of counter ions and solvent dose) fluctuate fluoride removal capacity of materials are reviewed. PMID:23497619
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CO2-Binding-Organic-Liquids-Enhanced CO2 Capture using Polarity-Swing-Assisted Regeneration
DOE Office of Scientific and Technical Information (OSTI.GOV)
Zhang, Jian; Kutnyakov, Igor; Koech, Phillip K.
A new solvent-based CO2 capture process couples the unique attributes of non-aqueous, CO2-binding organic liquids (CO2BOLs) with the newly discovered polarity-swing-assisted regeneration (PSAR) process that is unique to switchable ionic liquids. Laboratory measurements with PSAR indicate the ability to achieve a regeneration effect at 75°C comparable to that at 120°C using thermal regeneration only. Initial measurements also indicate that the kinetic behavior of CO2 release is also improved with PSAR. Abstract cleared PNWD-SA-9743
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Electrolytic orthoborate salts for lithium batteries
Angell, Charles Austen [Mesa, AZ; Xu, Wu [Tempe, AZ
2008-01-01
Orthoborate salts suitable for use as electrolytes in lithium batteries and methods for making the electrolyte salts are provided. The electrolytic salts have one of the formulae (I). In this formula anionic orthoborate groups are capped with two bidentate chelating groups, Y1 and Y2. Certain preferred chelating groups are dibasic acid residues, most preferably oxalyl, malonyl and succinyl, disulfonic acid residues, sulfoacetic acid residues and halo-substituted alkylenes. The salts are soluble in non-aqueous solvents and polymeric gels and are useful components of lithium batteries in electrochemical devices.
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Electrolytic orthoborate salts for lithium batteries
Angell, Charles Austen [Mesa, AZ; Xu, Wu [Tempe, AZ
2009-05-05
Orthoborate salts suitable for use as electrolytes in lithium batteries and methods for making the electrolyte salts are provided. The electrolytic salts have one of the formulae (I). In this formula anionic orthoborate groups are capped with two bidentate chelating groups, Y1 and Y2. Certain preferred chelating groups are dibasic acid residues, most preferably oxalyl, malonyl and succinyl, disulfonic acid residues, sulfoacetic acid residues and halo-substituted alkylenes. The salts are soluble in non-aqueous solvents and polymeric gels and are useful components of lithium batteries in electrochemical devices.
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ORGANIC SYNTHESES IN SOLVENT-FREE AND AQUEOUS MEDIA USING MICROWAVES
A solvent-free approach that involves microwave (MW) exposure of neat reactants (undiluted) catalyzed by the surfaces of recyclable mineral supports such as alumina, silica, clay, or 'doped' surfaces is presented which is applicable to a wide range of cleavage, condensation, cycl...
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Yang, Huachao; Yang, Jinyuan; Bo, Zheng; Chen, Xia; Shuai, Xiaorui; Kong, Jing; Yan, Jianhua; Cen, Kefa
2017-08-03
The chemical nature of electrolytes has been demonstrated to play a pivotal role in the charge storage of electric double-layer capacitors (EDLCs), whereas primary mechanisms are still partially resolved but controversial. In this work, a systematic exploration into EDL structures and kinetics of representative aqueous electrolytes is performed with numerical simulation and experimental research. Unusually, a novel charging mechanism exclusively predominated by kinetics is recognized, going beyond traditional views of manipulating capacitances preferentially via interfacial structural variations. Specifically, strikingly distinctive EDL structures stimulated by diverse ion sizes, valences, and mixtures manifest a virtually identical EDL capacitance, where the dielectric nature of solvents attenuates ionic effects on electrolyte redistributions, in stark contradiction with solvent-free counterpart and traditional Helmholtz theory. Meanwhile, corresponding kinetics evolve conspicuously with ionic species, intimately correlated with ion-solvent interactions. The achieved mechanisms are subsequently illuminated by electrochemical measurements, highlighting the crucial interplay between ions and solvents in regulating EDLC performances.
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Photo-dynamics of roseoflavin and riboflavin in aqueous and organic solvents
NASA Astrophysics Data System (ADS)
Zirak, P.; Penzkofer, A.; Mathes, T.; Hegemann, P.
2009-03-01
Roseoflavin (8-dimethylamino-8-demethyl- D-riboflavin) and riboflavin in aqueous and organic solvents are studied by optical absorption spectroscopy, fluorescence spectroscopy, and fluorescence decay kinetics. Solvent polarity dependent absorption shifts are observed. The fluorescence quantum yields are solvent dependent. For roseoflavin the fluorescence decay shows a bi-exponential dependence (ps to sub-ps time constant, and 100 ps to a few ns time constant). The roseoflavin photo-dynamics is explained in terms of fast intra-molecular charge transfer (diabatic electron transfer) from the dimethylamino electron donor group to the pteridin carbonyl electron acceptor followed by intra-molecular charge recombination. The fast fluorescence component is due to direct locally-excited-state emission, and the slow fluorescence component is due to delayed locally-excited-state emission and charge transfer state emission. The fluorescence decay of riboflavin is mono-exponential. The S 1-state potential energy surface is determined by vibronic relaxation and solvation dynamics due to excited-state dipole moment changes (adiabatic optical electron transfer).
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Comparison of polymer induced and solvent induced trypsin denaturation: the role of hydrophobicity.
Jasti, Lakshmi S; Fadnavis, Nitin W; Addepally, Uma; Daniels, Siona; Deokar, Sarika; Ponrathnam, Surendra
2014-04-01
Trypsin adsorption from aqueous buffer by various copolymers of allyl glycidyl ether-ethylene glycol dimethacrylate (AGE-EGDM) copolymer with varying crosslink density increases with increasing crosslink density and the effect slowly wears off after reaching a plateau at 50% crosslink density. The copolymer with 25% crosslink density was reacted with different amines with alkyl/aryl side chains to obtain a series of copolymers with 1,2-amino alcohol functional groups and varying hydrophobicity. Trypsin binding capacity again increases with hydrophobicity of the reacting amine and a good correlation between logPoctanol of the amine and protein binding is observed. The bound trypsin is denatured to the extent of 90% in spite of the presence of hydrophilic hydroxyl and amino groups. The behavior was comparable to that in mixtures of aqueous buffer and water-miscible organic co-solvents where the solvent concentration required to deactivate 50% of the enzyme (C50) is dependent on logPoctanol of the co-solvent. Copyright © 2014 Elsevier B.V. All rights reserved.
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Shao, Feng; Gu, Lifei; Chen, Huijuan; Liu, Ronghua; Huang, Huilian; Ren, Gang
2016-01-01
Background: Hawthorn (Crataegus pinnatifida) is a Chinese medicinal plant traditionally used in the treatment of hyperlipidemia. Recently, studies indicated free radical scavenging was one of the major pathways to alleviate hyperlipidemia. Moreover, hawthorn fruit is a rich source of phenols, which quench free radical and attenuate hyperlipidemia. However, the phenols vary with processing methods, especially solvent type. Objective: Our aim was to compare hypolipidemic and antioxidant effects of aqueous and ethanol extracts of hawthorn fruit in hyperlipidemia rats. Materials and Methods: After a 4-week treatment of high-fat emulsion, lipid profile levels and antioxidant levels of two extracts were determined using commercial analysis. Total phenols content in the extract of hawthorn fruit was determined colorimetrically by the Folin–Ciocalteu method. Results: Both ethanol and aqueous extracts of hawthorn fruit possessed hypolipidemic and antioxidant activities. Simultaneously, stronger activities were observed in ethanol extract. Besides, total phenols content in ethanol extract from the same quality of hawthorn fruit was 3.9 times more than that in aqueous extract. Conclusion: The obvious difference of hypolipidemic and antioxidant effects between ethanol extract and aqueous extract of hawthorn fruit was probably due to the presence of total phenols content, under the influence of extraction solvent. SUMMARY Ethanol extract of hawthorn fruit exhibited more favorable hypolipidemic and antioxidant effects than aqueous extract. The higher effects could be due to the higher content of total phenols that varies with extraction solvent. Abbreviations used: TC: Total cholesterol, TG: Triglyceride, LDL-C: Low-density lipoprotein cholesterol, HDL-C: High-density lipoprotein cholesterol, GSH-Px: Glutathione peroxidase, SOD: Superoxide dismutase, MDA: Malondialdehyde, CAT: Catalase, NO: Nitric oxide, NOS: Nitric oxide synthase, SR-BI: Scavenger receptor Class B Type I PMID:27019563
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Shao, Feng; Gu, Lifei; Chen, Huijuan; Liu, Ronghua; Huang, Huilian; Ren, Gang
2016-01-01
Hawthorn (Crataegus pinnatifida) is a Chinese medicinal plant traditionally used in the treatment of hyperlipidemia. Recently, studies indicated free radical scavenging was one of the major pathways to alleviate hyperlipidemia. Moreover, hawthorn fruit is a rich source of phenols, which quench free radical and attenuate hyperlipidemia. However, the phenols vary with processing methods, especially solvent type. Our aim was to compare hypolipidemic and antioxidant effects of aqueous and ethanol extracts of hawthorn fruit in hyperlipidemia rats. After a 4-week treatment of high-fat emulsion, lipid profile levels and antioxidant levels of two extracts were determined using commercial analysis. Total phenols content in the extract of hawthorn fruit was determined colorimetrically by the Folin-Ciocalteu method. Both ethanol and aqueous extracts of hawthorn fruit possessed hypolipidemic and antioxidant activities. Simultaneously, stronger activities were observed in ethanol extract. Besides, total phenols content in ethanol extract from the same quality of hawthorn fruit was 3.9 times more than that in aqueous extract. The obvious difference of hypolipidemic and antioxidant effects between ethanol extract and aqueous extract of hawthorn fruit was probably due to the presence of total phenols content, under the influence of extraction solvent. Ethanol extract of hawthorn fruit exhibited more favorable hypolipidemic and antioxidant effects than aqueous extract. The higher effects could be due to the higher content of total phenols that varies with extraction solvent. Abbreviations used: TC: Total cholesterol, TG: Triglyceride, LDL-C: Low-density lipoprotein cholesterol, HDL-C: High-density lipoprotein cholesterol, GSH-Px: Glutathione peroxidase, SOD: Superoxide dismutase, MDA: Malondialdehyde, CAT: Catalase, NO: Nitric oxide, NOS: Nitric oxide synthase, SR-BI: Scavenger receptor Class B Type I.
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Hyde, E.K.; Katzin, L.I.; Wolf, M.J.
1959-07-14
The separation of uranium from a mixture of uranium and thorium by organic solvent extraction from an aqueous solution is described. The uranium is separrted from an aqueous mixture of uranium and thorium nitrates 3 N in nitric acid and containing salting out agents such as ammonium nitrate, so as to bring ihe total nitrate ion concentration to a maximum of about 8 N by contacting the mixture with an immiscible aliphatic oxygen containing organic solvent such as diethyl carbinol, hexone, n-amyl acetate and the like. The uranium values may be recovered from the organic phase by back extraction with water.
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Schmieding, E.G.; Ruehle, A.E.
1961-04-11
A method is given for extracting metal values from an aqueous feed wherein the aqueous feed is passed countercurrent to an organic extractant through a plurality of decanting zones and a portion of the mixture contained in each decanting zone is recycled through a mixing zone associated therewith. The improvement consists of passing more solvent from the top of one decanting zone to the bottom of the preceding decanting zone than can rise to the top thereof and recycling that portion of the solvent that does not rise to the top back to the first named decanting zone through its associated mixing zone.
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SEPARATION OF URANIUM FROM ZIRCONIUM AND NIOBIUM BY SOLVENT EXTRACTION
Voiland, E.E.
1958-05-01
A process for separation of the uranium from zirconium and/or niobium values contained in 3 to 7M aqueous nitric acid solutions is described. This is accomplished by adding phosphoric acid anions to the nitric acid solution containing the uranium, zirconium, and/or niobium in an amount sufficient to make the solution 0.05 to 0.2M in phosphate ion and contacting the solution with an organic water-immiscible solvent such as MEK, whereby the uranyl values are taken up by the extract phase while the zirconium and niobium preferentially remain in the aqueous raffinate.
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Mozhaev, V V; Sergeeva, M V; Belova, A B; Khmelnitsky, Y L
1990-03-25
Inactivation of alpha-chymotrypsin in aqueous solutions of alcohols and diols proceeds both reversibly and irreversibly. Reversible loss of the specific enzyme activity results from conformational changes (unfolding) of the enzyme detected by fluorescence spectroscopy. Multipoint covalent attachment to the matrix of polyacryl-amide gel by copolymerization method stabilizes alpha-chymotrypsin from denaturation by alcohols, the stabilizing effect increasing with the number of bonds between the protein and the support. Immobilization protects the enzyme also from irreversible inactivation by organic solvents resulting from bimolecular aggregation and autolysis.
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Tokudome, Yasuaki; Morimoto, Tsuyoshi; Tarutani, Naoki; Vaz, Pedro D; Nunes, Carla D; Prevot, Vanessa; Stenning, Gavin B G; Takahashi, Masahide
2016-05-24
Increasing attention has been dedicated to the development of nanomaterials rendering green and sustainable processes, which occur in benign aqueous reaction media. Herein, we demonstrate the synthesis of another family of green nanomaterials, layered double hydroxide (LDH) nanoclusters, which are concentrated (98.7 g/L in aqueous solvent), stably dispersed (transparent sol for >2 weeks), and catalytically active colloids of nano LDHs (isotropic shape with the size of 7.8 nm as determined by small-angle X-ray scattering). LDH nanoclusters are available as colloidal building blocks to give access to meso- and macroporous LDH materials. Proof-of-concept applications revealed that the LDH nanocluster works as a solid basic catalyst and is separable from solvents of catalytic reactions, confirming the nature of nanocatalysts. The present work closely investigates the unique physical and chemical features of this colloid, the formation mechanism, and the ability to act as basic nanocatalysts in benign aqueous reaction systems.
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In Situ Cross-Linking of Polyvinyl Alcohol Films
NASA Technical Reports Server (NTRS)
Philipp, W. H.; Shu, L. C.; May, C. E.
1984-01-01
Films or impregnated matrices readily made from aqueous polyvinyl alcohol solution. Controlled thickness films made by casting precise quantities of aqueous polymer solution on smooth surface, allowing water to evaporate and then removing film. Composite separators formed in similar fashion by impregnating cloth matrix with polyvinyl alcohol solution and drying composite. Insoluble thin hydrophilic membranes made from aqueous systems, and use of undesirable organic solvents not required.
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Stabilized aqueous foam systems and concentrate and method for making them
Rand, Peter B.
1984-01-01
This invention comprises a combination of a water soluble polymer of the polyacrylic acid type, a foam stabilizer of dodecyl alcohol, a surfactant, a solvent and water as a concentrate for use in producing stabilized aqueous foams. In another aspect, the invention comprises a solution of the concentrate with water. In still another aspect the invention includes a method of generating stabilized aqueous foams.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Weiland, R.H.; Dingman, J.C.; Cronin, D.B.
1997-09-01
New data are reported on the heat capacity of CO{sub 2}-loaded, aqueous solutions of monoethanolamine (MEA), diethanolamine (DEA), N-methyldiethanolamine (MDEA), and aqueous MDEA-based blends with MEA and DEA. The work reported here was motivated by the need to quantify the effect of acid gas loading on the important physical properties of gas-sweetening solvents.
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Aqueous process for recovering sulfur from hydrogen sulfide-bearing gas
Basu, Arunabha
2015-05-05
A process for recovering sulfur from a hydrogen sulfide-bearing gas utilizes an aqueous reaction medium, a temperature of about 110-150.degree. C., and a high enough pressure to maintain the aqueous reaction medium in a liquid state. The process reduces material and equipment costs and addresses the environmental disadvantages associated with known processes that rely on high boiling point organic solvents.
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'GREENER' CHEMICAL SYNTHESES USING MICROWAVES UNDER SOLVENT-FREE CONDITIONS OR AQUEOUS MEDIA
A solvent-free approach that involves microwave (MW) exposure of neat reactants (undiluted) catalyzed by the surfaces of recyclable mineral supports such as alumina, silica, clay, or 'doped' surfaces is presented which is applicable to a wide range of cleavage, condensation, cycl...
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Cantu, Marcelo Delmar; Hillebranda, Sandro; Carrilho, Emanuel
2005-03-11
Non-aqueous capillary electrophoresis (NACE) may provide a selectivity enhancement in separations since the analyte dissociation constants (pKa) in organic media are different from those in aqueous solutions. In this work, we have studied the inversion in mobility order observed in the separation of tertiary (imipramine (IMI) and amitryptiline (AMI)) and secondary amines (desipramine (DES) and nortryptiline (NOR)) in water, methanol, and acetonitrile. We have determined the pKa values in those solvents and the variation of dissociation constants with the temperature. From these data, and applying the Van't Hoff equation, we have calculated the thermodynamic parameters deltaH and deltaS. The pKa values found in methanol for DES, NOR, IMI, and AMI were 10.80, 10.79, 10.38, and 10.33, respectively. On the other hand, in acetonitrile an opposite relation was found since the values were 20.60, 20.67, 20.74, and 20.81 for DES, NOR, IMI, and AMI. This is the reason why a migration order inversion is observed in NACE for these solvents. The thermodynamic parameters were evaluated and presented a tendency that can be correlated with that observed for pKa values.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Mathias, Paul M.; Zheng, Feng; Heldebrant, David J.
2015-09-17
The kinetics of the absorption of CO 2 into two nonaqueous CO 2-binding organic liquid (CO 2BOL) solvents were measured at T=35, 45, and 55 °C with a wetted-wall column. Selected CO 2 loadings were run with a so-called “first-generation” CO 2BOL, comprising an independent base and alcohol, and a “second-generation” CO 2BOL, in which the base and alcohol were conjoined. Liquid-film mass-transfer coefficient (k'g) values for both solvents were measured to be comparable to values for monoethanolamine and piperazine aqueous solvents under a comparable driving force, in spite of far higher solution viscosities. An inverse temperature dependence of themore » k'g value was also observed, which suggests that the physical solubility of CO 2 in organic liquids may be making CO 2 mass transfer faster than expected. Aspen Plus software was used to model the kinetic data and compare the CO 2 absorption behavior of nonaqueous solvents with that of aqueous solvent platforms. This work continues our development of the CO2BOL solvents. Previous work established the thermodynamic properties related to CO 2 capture. The present paper quantitatively studies the kinetics of CO 2 capture and develops a rate-based model.« less
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Dramatic enhancement of enzymatic activity in organic solvents by lyoprotectants
DOE Office of Scientific and Technical Information (OSTI.GOV)
Dabulis, K.; Klibanov, A.M.
1993-03-05
When seven different hydrolytic enzymes (four proteases and three lipases) were lyophilized from aqueous solution containing a ligand, N-Ac-L-Phe-NH[sub 2], their catalytic activity in anhydrous solvents was far greater (one to two orders of magnitude) than that of the enzymes lyophilized without the ligand. This ligand-induced activation was expressed regardless of whether the substrate employed in organic solvents structurally resembled the ligand. Furthermore, nonligand lyoprotectants [sorbitol, other sugars, and poly(ethylene glycol)] also dramatically enhanced enzymatic activity in anhydrous solvents when present in enzyme aqueous solution prior to lyophilization. The effects of the ligand and of the lyoprotectants were nonadditive, suggestingmore » the same mechanism of action. Excipient-activated and nonactivated enzymes exhibited identical activities in water. Also, addition of the excipients directly to suspensions of nonactivated enzymes in organic solvents had no appreciable effect on catalytic activity. These observations indicate that the mechanism of the excipient-induced activation is based on the ability of the excipients to alleviate reversible denaturation of enzymes upon lyophilization. Activity enhancement induced by the excipients is displayed even after their removal by washing enzymes with anhydrous solvents. Subtilisin Carlsberg, lyophilized with sorbitol, was found to be a much more efficient practical catalyst than its regular' counterpart.« less
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Doppler, Maria; Kluger, Bernhard; Bueschl, Christoph; Schneider, Christina; Krska, Rudolf; Delcambre, Sylvie; Hiller, Karsten; Lemmens, Marc; Schuhmacher, Rainer
2016-01-01
The evaluation of extraction protocols for untargeted metabolomics approaches is still difficult. We have applied a novel stable isotope-assisted workflow for untargeted LC-HRMS-based plant metabolomics , which allows for the first time every detected feature to be considered for method evaluation. The efficiency and complementarity of commonly used extraction solvents, namely 1 + 3 (v/v) mixtures of water and selected organic solvents (methanol, acetonitrile or methanol/acetonitrile 1 + 1 (v/v)), with and without the addition of 0.1% (v/v) formic acid were compared. Four different wheat organs were sampled, extracted and analysed by LC-HRMS. Data evaluation was performed with the in-house-developed MetExtract II software and R. With all tested solvents a total of 871 metabolites were extracted in ear, 785 in stem, 733 in leaf and 517 in root samples, respectively. Between 48% (stem) and 57% (ear) of the metabolites detected in a particular organ were found with all extraction mixtures, and 127 of 996 metabolites were consistently shared between all extraction agent/organ combinations. In aqueous methanol, acidification with formic acid led to pronounced pH dependency regarding the precision of metabolite abundance and the number of detectable metabolites, whereas extracts of acetonitrile-containing mixtures were less affected. Moreover, methanol and acetonitrile have been found to be complementary with respect to extraction efficiency. Interestingly, the beneficial properties of both solvents can be combined by the use of a water-methanol-acetonitrile mixture for global metabolite extraction instead of aqueous methanol or aqueous acetonitrile alone. PMID:27367667
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NASA Astrophysics Data System (ADS)
Bruce, Ellen E.; van der Vegt, Nico F. A.
2018-06-01
Non-polarizable force fields for hydrated ions not always accurately describe short-range ion-ion interactions, frequently leading to artificial ion clustering in bulk aqueous solutions. This can be avoided by adjusting the nonbonded anion-cation or cation-water Lennard-Jones parameters. This approach has been successfully applied to different systems, but the parameterization is demanding owing to the necessity of separate investigations of each ion pair. Alternatively, polarization effects may effectively be accounted for using the electronic continuum correction (ECC) of Leontyev et al. [J. Chem. Phys. 119, 8024 (2003)], which involves scaling the ionic charges with the inverse square-root of the water high-frequency dielectric permittivity. ECC has proven to perform well for monovalent salts as well as for divalent salts in water. Its performance, however, for multivalent salts with higher valency remains unexplored. The present work illustrates the applicability of the ECC model to trivalent K3PO4 and divalent K2HPO4 in water. We demonstrate that the ECC models, without additional tuning of force field parameters, provide an accurate description of water-mediated interactions between salt ions. This results in predictions of the osmotic coefficients of aqueous K3PO4 and K2HPO4 solutions in good agreement with experimental data. Analysis of ion pairing thermodynamics in terms of contact ion pair (CIP), solvent-separated ion pair, and double solvent-separated ion pair contributions shows that potassium-phosphate CIP formation is stronger with trivalent than with divalent phosphate ions.
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Ramanathan, K; Jönsson, B R; Danielsson, B
2000-08-01
The stability of horseradish peroxidase (HRP) in aqueous and organic solvents is applied to develop a simple thermometric procedure to detect the binding of retinoic acid-HRP conjugate to retinol binding protein (RBP). Butanone peroxide (BP) in organic phase and hydrogen peroxide in aqueous phase is detected thermometrically on a HRP column, immobilized by cross-linking with glutaraldehyde on controlled pore glass (CPG). Acetone, acetonitrile, methanol, and 2-butanol are used for detection of BP, in the flow injection analysis (FIA) mode. A linear range between 1 and 50 mM BP is obtained in all the organic solvents with a precision of 5-7% (CV%). The magnitude and nature of the thermometric response is significantly different in each organic solvent. The stability of HRP in the organic phase is used to study the stability of a retinoic acid-HRP conjugate bound to immobilized RBP. The response of HRP (to 20 mM BP) in the retinoic acid-HRP conjugate is used as an indicator of the stability of the RBP-retinoic acid-HRP complex, after challenges with various organic/aqueous solvents. Both immobilized HRP and RBP are stable at least for 6 months. The effect of o-phenylene diamine on the thermometric response of HRP is also investigated. A scheme for the design of a thermometric retinol (vitamin A) biosensor is proposed.
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Microbial solubilization of phosphate
Rogers, R.D.; Wolfram, J.H.
1993-10-26
A process is provided for solubilizing phosphate from phosphate containing ore by treatment with microorganisms which comprises forming an aqueous mixture of phosphate ore, microorganisms operable for solubilizing phosphate from the phosphate ore and maintaining the aqueous mixture for a period of time and under conditions operable to effect the microbial solubilization process. An aqueous solution containing soluble phosphorus can be separated from the reacted mixture by precipitation, solvent extraction, selective membrane, exchange resin or gravity methods to recover phosphate from the aqueous solution. 6 figures.
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Microbial solubilization of phosphate
Rogers, Robert D.; Wolfram, James H.
1993-01-01
A process is provided for solubilizing phosphate from phosphate containing ore by treatment with microorganisms which comprises forming an aqueous mixture of phosphate ore, microorganisms operable for solubilizing phosphate from the phosphate ore and maintaining the aqueous mixture for a period of time and under conditions operable to effect the microbial solubilization process. An aqueous solution containing soluble phosphorous can be separated from the reacted mixture by precipitation, solvent extraction, selective membrane, exchange resin or gravity methods to recover phosphate from the aqueous solution.
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Lipase biofilm deposited by Matrix Assisted Pulsed Laser Evaporation technique
NASA Astrophysics Data System (ADS)
Aronne, Antonio; Bloisi, Francesco; Calabria, Raffaela; Califano, Valeria; Depero, Laura E.; Fanelli, Esther; Federici, Stefania; Massoli, Patrizio; Vicari, Luciano R. M.
2015-05-01
Lipase is an enzyme that finds application in biodiesel production and for detection of esters and triglycerides in biosensors. Matrix Assisted Pulsed Laser Evaporation (MAPLE), a technique derived from Pulsed Laser Deposition (PLD) for deposition of undamaged biomolecules or polymers, is characterized by the use of a frozen target obtained from a solution/suspension of the guest material (to be deposited) in a volatile matrix (solvent). The presence of the solvent avoids or at least reduces the potential damage of guest molecules by laser radiation but only the guest material reaches the substrate in an essentially solvent-free deposition. MAPLE can be used for enzymes immobilization, essential for industrial application, allowing the development of continuous processes, an easier separation of products, the reuse of the catalyst and, in some cases, enhancing enzyme properties (pH, temperature stability, etc.) and catalytic activity in non-aqueous media. Here we show that MAPLE technique can be used to deposit undamaged lipase and that the complex structure (due to droplets generated during extraction from target) of the deposited material can be controlled by changing the laser beam fluence.
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Surfactant/Supercritical Fluid Cleaning of Contaminated Substrates
NASA Technical Reports Server (NTRS)
White, Gary L.
1997-01-01
CFC's and halogenated hydrocarbon solvents have been the solvents of choice to degrease and otherwise clean precision metal parts to allow proper function. Recent regulations have, however, rendered most of these solvents unacceptable for these purposes. New processes which are being used or which have been proposed to replace these solvents usually either fail to remove water soluble contaminants or produce significant aqueous wastes which must then be disposed of. In this work, a new method for cleaning surfaces will be investigated. Solubility of typical contaminants such as lubricating greases and phosphatizing bath residues will be studied in several surfactant/supercritical fluid solutions. The effect of temperature, pressure, and the composition of the cleaning mixture on the solubility of oily, polar, and ionic contaminants will be investigated. A reverse micellar solution in a supercritical light hydrocarbon solvent will be used to clean samples of industrial wastes. A reverse micellar solution is one where water is dissolved into a non-polar solvent with the aid of a surfactant. The solution will be capable of dissolving both water-soluble contaminants and oil soluble contaminants. Once the contaminants have been dissolved into the solution they will be separated from the light hydrocarbon and precipitated by a relatively small pressure drop and the supercritical solvent will be available for recycle for reuse. The process will be compared to the efficacy of supercritical CO2 cleaning by attempting to clean the same types of substrates and machining wastes with the same contaminants using supercritical CO2. It is anticipated that the supercritical CO2 process will not be capable of removing ionic residues.
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ELECTROLYTIC SOLUTIONS. Annual Progress Report, May 1, 1962-June 1, 1963
DOE Office of Scientific and Technical Information (OSTI.GOV)
Braunstein, J.
Results of investigations of the thermodynamics of association in molten salts and in concentrated aqueous electrolyte solutions are reported. Association constants of Pb(II) with chloride or bromide and of Cd(II) with chloride or bromide in molten mixtures of LiNC/sub 3/ and KNO/sub 3/ were measured potentiometrically at several temperatures and compared with previous results in mixtures of NaNO/sub 3/ and KNO/sub 3/. The anomalous'' solvent effect of lithium ion, reported previously for the association of Cd(II) with bromide was observed aiso for the other associations and a tentative explanation is suggested. The temperature dependence of the association constants was foundmore » to be in agreement with the quasi-lattice model. The association constant of Ag(I) with iodide in molten mixtures of NaNO/sub 3/ and KNO/sub 3/ was measured and compared with previous results in pure KNO/sub 3/. The solvent effect was consistent with the reciprocal coulomb effect.'' Techniques were developed, and preliminary results obtained for measuring association constants in the solvent system KNO/sub 3/--Ca(NO/sub 3/)/sub 2/ in order to investigate the effect of charge as well as size of solvent cation on association constants in molten salt solutions. The measurement of association constants in concentrated aqueous electrolyte solutions was continued. The association of Cd(II) with bromide in aqueous LiNC/sub 3/ was measured as part of a program to find a system that would lend itself to investigation over the range between anhydrous molten salt and aqueous electrolyte solution. Cells and electrodes were developed for investigating association constants in equimolar LiNO/sub 3/ -KNO/sub 3/ with controlled small water contents, and preliminary results are reported. (auth)« less
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Yang, Jing-Hua; Shao, Jing; Wang, Hou-Yu; Dong, Jing-Yu; Fan, Liu-Yin; Cao, Cheng-Xi; Xu, Yu-Quan
2012-09-01
Herein, a simple novel free-flow electrophoresis (FFE) method was developed via introduction of organic solvent into the electrolyte system, increasing the solute solubility and throughput of the sample. As a proof of concept, phenazine-1-carboxylic acid (PCA) from Pseudomonas sp. M18 was selected as a model solute for the demonstration on feasibility of novel FFE method on account of its faint solubility in aqueous circumstance. In the developed method, the organic solvent was added into not only the sample buffer to improve the solubility of the solute, but also the background buffer to construct a uniform aqueous-organic circumstance. These factors of organic solvent percentage and types as well as pH value of background buffer were investigated for the purification of PCA in the FFE device via CE. The experiments revealed that the percentage and the types of organic solvent exerted major influence on the purification of PCA. Under the optimized conditions (30 mM phosphate buffer in 60:40 (v/v) water-methanol at an apparent pH 7.0, 3.26 mL/min background flux, 10-min residence time of injected sample, and 400 V), PCA could be continuously purified from its impurities. The flux of sample injection was 10.05 μL/min, and the recovery was up to 93.7%. An 11.9-fold improvement of throughput was found with a carrier buffer containing 40% (v/v) methanol, compared with the pure aqueous phase. The developed procedure is of evident significance for the purification of weak polarity solute via FFE. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Holehouse, Alex S.; Garai, Kanchan; Lyle, Nicholas; Vitalis, Andreas; Pappu, Rohit V.
2015-01-01
In aqueous solutions with high concentrations of chemical denaturants such as urea and guanidinium chloride (GdmCl) proteins expand to populate heterogeneous conformational ensembles. These denaturing environments are thought to be good solvents for generic protein sequences because properties of conformational distributions align with those of canonical random coils. Previous studies showed that water is a poor solvent for polypeptide backbones and therefore backbones form collapsed globular structures in aqueous solvents. Here, we ask if polypeptide backbones can intrinsically undergo the requisite chain expansion in aqueous solutions with high concentrations of urea and GdmCl. We answer this question using a combination of molecular dynamics simulations and fluorescence correlation spectroscopy. We find that the degree of backbone expansion is minimal in aqueous solutions with high concentrations denaturants. Instead, polypeptide backbones sample conformations that are denaturant-specific mixtures of coils and globules, with a persistent preference for globules. Therefore, typical denaturing environments cannot be classified as good solvents for polypeptide backbones. How then do generic protein sequences expand in denaturing environments? To answer this question, we investigated the effects of sidechains using simulations of two archetypal sequences with amino acid compositions that are mixtures of charged, hydrophobic, and polar groups. We find that sidechains lower the effective concentration of backbone amides in water leading to an intrinsic expansion of polypeptide backbones in the absence of denaturants. Additional dilution of the effective concentration of backbone amides is achieved through preferential interactions with denaturants. These effects lead to conformational statistics in denaturing environments that are congruent with those of canonical random coils. Our results highlight the role of sidechain-mediated interactions as determinants of the conformational properties of unfolded states in water and in influencing chain expansion upon denaturation. PMID:25664638
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Modeling the antisymmetric and symmetric stretching vibrational modes of aqueous carboxylate anions
NASA Astrophysics Data System (ADS)
Sutton, Catherine C. R.; Franks, George V.; da Silva, Gabriel
2015-01-01
The infrared spectra of six aqueous carboxylate anions have been calculated at the M05-2X/cc-pVTZ level of theory with the SMD solvent model, and validated against experimental data from the literature over the region of 1700 cm-1 to 1250 cm-1; this region corresponds to the stretching modes of the carboxylate group, and is often interrogated when probing bonding of carboxylates to other species and surfaces. The anions studied here were formate, acetate, oxalate, succinate, glutarate and citrate. For the lowest energy conformer of each anion, the carboxylate moiety antisymmetric stretching peak was predicted with a mean signed error of only 4 cm-1 using the SMD solvent model, while the symmetric peak was slightly overestimated. Performing calculations in vacuum and scaling was found to generally over-predict the antisymmetric vibrational frequencies and under predict the symmetric peak. Different conformers of the same anion were found to have only slightly different spectra in the studied region and the inclusion of explicit water molecules was not found to significantly change the calculated spectra when the implicit solvent model is used. Overall, the use of density functional theory in conjunction with an implicit solvent model was found to result in infra-red spectra that are the best reproduction of the features found experimentally for the aqueous carboxylate ions in the important 1700 cm-1 to 1250 cm-1 region. The development of validated model chemistries for simulating the stretching modes of aqueous carboxylate ions will be valuable for future studies that investigate how carboxylate anions complex with multivalent metal cations and related species in solution.
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Microcapsules fabricated from liquid marbles stabilized with latex particles.
Ueno, Kazuyuki; Hamasaki, Sho; Wanless, Erica J; Nakamura, Yoshinobu; Fujii, Syuji
2014-03-25
Millimeter- and centimeter-sized "liquid marbles" were readily prepared by rolling water droplets on a powder bed of dried submicrometer-sized polystyrene latex particles carrying poly[2-(diethylamino)ethyl methacrylate] hairs (PDEA-PS). Scanning electron microscopy studies indicated that flocs of the PDEA-PS particles were adsorbed at the surface of these water droplets, leading to stable spherical liquid marbles. The liquid marbles were deformed as a result of water evaporation to adopt a deflated spherical geometry, and the rate of water evaporation decreased with increasing atmospheric relative humidity. Conversely, liquid marbles formed using saturated aqueous LiCl solution led to atmospheric water absorption by the liquid marbles and a consequent mass increase. The liquid marbles can be transformed into polymeric capsules containing water by exposure to solvent vapor: the PDEA-PS particles were plasticized with the solvent vapor to form a polymer film at the air-water interface of the liquid marbles. The polymeric capsules with aqueous volumes of 250 μL or less kept their oblate ellipsoid/near spherical shape even after complete water evaporation, which confirmed that a rigid polymeric capsule was successfully formed. Both the rate of water evaporation from the pure water liquid marbles and the rate of water adsorption into the aqueous LiCl liquid marbles were reduced with an increase of solvent vapor treatment time. This suggests that the number and size of pores within the polymer particles/flocs on the liquid marble surface decreased due to film formation during exposure to organic solvent vapor. In addition, organic-inorganic composite capsules and colloidal crystal capsules were fabricated from liquid marbles containing aqueous SiO2 dispersions.
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Solubilities of carbon dioxide in aqueous potassium carbonate solutions mixed with physical solvents
DOE Office of Scientific and Technical Information (OSTI.GOV)
Park, S.B.; Lee, H.; Lee, K.H.
1998-09-01
The removal of acidic gases such as CO{sub 2}, H{sub 2}S, and COS from gas streams is a very important operation for petrochemical, oil refineries, ammonia manufacture, coal gasification, and natural gas purification plants. Here, the solubilities of carbon dioxide in aqueous potassium carbonate (K{sub 2}CO{sub 3}) solutions mixed with physical solvents were measured at 298.2 and 323.2 K with a CO{sub 2} partial-pressure range of 5 kPa to 2 MPa. 1,2-propanediol and propylene carbonate were selected as physical solvents. The aqueous solutions treated in this study were 5 mass% K{sub 2}CO{sub 3}-15 mass% 1,2-propanediol and propylene carbonate were selectedmore » as physical solvents. The aqueous solutions treated in this study were 5 mass% K{sub 2}CO{sub 3}-15 mass% propylene carbonate. The experimental solubility results were presented by the mole ratio of CO{sub 2} and K{sub 2}CO{sub 3} contained in the liquid mixture. The addition of 1,2-propanediol to 5 mass% K{sub 2}CO{sub 3} solution lowered the solubility of CO{sub 2} at constant temperature and pressure conditions when CO{sub 2} partial-pressure range of 5 kPa to 2 MPa. In the case of propylene carbonate the addition of propylene carbonate increased the experimental solubilities in the region of low CO{sub 2} partial pressures and decreased as the CO{sub 2} partial pressure was increased above atmospheric. The solubilities of CO{sub 2} decreased with increasing temperature in the range of 298.2 to 323.2 K.« less
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A poly(vinyl alcohol)/sodium alginate blend monolith with nanoscale porous structure
2013-01-01
A stimuli-responsive poly(vinyl alcohol) (PVA)/sodium alginate (SA) blend monolith with nanoscale porous (mesoporous) structure is successfully fabricated by thermally impacted non-solvent induced phase separation (TINIPS) method. The PVA/SA blend monolith with different SA contents is conveniently fabricated in an aqueous methanol without any templates. The solvent suitable for the fabrication of the present blend monolith by TINIPS is different with that of the PVA monolith. The nanostructural control of the blend monolith is readily achieved by optimizing the fabrication conditions. Brunauer Emmett Teller measurement shows that the obtained blend monolith has a large surface area. Pore size distribution plot for the blend monolith obtained by the non-local density functional theory method reveals the existence of the nanoscale porous structure. Fourier transform infrared analysis reveals the strong interactions between PVA and SA. The pH-responsive property of the blend monolith is investigated on the basis of swelling ratio in different pH solutions. The present blend monolith of biocompatible and biodegradable PVA and SA with nanoscale porous structure has large potential for applications in biomedical and environmental fields. PMID:24093494
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A poly(vinyl alcohol)/sodium alginate blend monolith with nanoscale porous structure.
Sun, Xiaoxia; Uyama, Hiroshi
2013-10-04
A stimuli-responsive poly(vinyl alcohol) (PVA)/sodium alginate (SA) blend monolith with nanoscale porous (mesoporous) structure is successfully fabricated by thermally impacted non-solvent induced phase separation (TINIPS) method. The PVA/SA blend monolith with different SA contents is conveniently fabricated in an aqueous methanol without any templates. The solvent suitable for the fabrication of the present blend monolith by TINIPS is different with that of the PVA monolith. The nanostructural control of the blend monolith is readily achieved by optimizing the fabrication conditions. Brunauer Emmett Teller measurement shows that the obtained blend monolith has a large surface area. Pore size distribution plot for the blend monolith obtained by the non-local density functional theory method reveals the existence of the nanoscale porous structure. Fourier transform infrared analysis reveals the strong interactions between PVA and SA. The pH-responsive property of the blend monolith is investigated on the basis of swelling ratio in different pH solutions. The present blend monolith of biocompatible and biodegradable PVA and SA with nanoscale porous structure has large potential for applications in biomedical and environmental fields.
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Kann, Z R; Skinner, J L
2014-09-14
Non-polarizable models for ions and water quantitatively and qualitatively misrepresent the salt concentration dependence of water diffusion in electrolyte solutions. In particular, experiment shows that the water diffusion coefficient increases in the presence of salts of low charge density (e.g., CsI), whereas the results of simulations with non-polarizable models show a decrease of the water diffusion coefficient in all alkali halide solutions. We present a simple charge-scaling method based on the ratio of the solvent dielectric constants from simulation and experiment. Using an ion model that was developed independently of a solvent, i.e., in the crystalline solid, this method improves the water diffusion trends across a range of water models. When used with a good-quality water model, e.g., TIP4P/2005 or E3B, this method recovers the qualitative behaviour of the water diffusion trends. The model and method used were also shown to give good results for other structural and dynamic properties including solution density, radial distribution functions, and ion diffusion coefficients.
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RECOVERY OF URANIUM BY AROMATIC DITHIOCARBAMATE COMPLEXING
Neville, O.K.
1959-08-11
A selective complexing organic solvent extraction process is presented for the separation of uranium values from an aqueous nitric acid solution of neutron irradiated thorium. The process comprises contacting the solution with an organic aromatic dithiccarbamaie and recovering the resulting urancdithiccarbamate complex with an organic solvent such as ethyl acetate.
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Structure of Porous Starch Microcellular Foam Particles
USDA-ARS?s Scientific Manuscript database
A relatively new starch product with various novel applications is a porous microcellular foam. The foam product is made by dehydrating a starch hydrogel in a solvent such as ethanol and then removing the solvent to form a foam product. The process involves heating an aqueous slurry of starch (8% w/...
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A solvent-free approach that involves microwave (MW) exposure of neat reactants (undiluted) catalyzed by the surfaces of recyclable mineral supports such as alumina, silica, clay, or 'doped' surfaces is presented which is applicable to a wide range of cleavage, condensation, cycl...
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Multiple Solvent Extraction System with Flow Injection Technology.
1981-09-30
encounters a back extraction step where the direction of the extraction is from organic to aqueous solvent. Thus it is advantageous to incorporate both...stainless steel ( Alltech Associates, Arlington Heights, IQ) and prepared from a single section of 180 cmn in length. The Section 2 mixing and extraction
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Lovrić, Vanja; Putnik, Predrag; Kovačević, Danijela Bursać; Jukić, Marijana; Dragović-Uzelac, Verica
2017-06-01
This research was undertaken to investigate the influence of extraction parameters during microwave-assisted extraction on total phenolic content, total flavonoids, total hydroxycinnamic acids and total flavonols of blackthorn flowers as well as to evaluate the antioxidant capacity by two different methods (2,2-diphenyl-1-picrylhydrazyl free radical scavenging capacity and ferric reducing antioxidant power assays). The investigated extraction parameters were: solvent type and volume fraction of alcohol in solvent (50 and 70% aqueous solutions of ethanol and methanol), extraction time (5, 15 and 25 min) and extraction temperature (40, 50 and 60 °C) controlled by microwave power of 100, 200 and 300 W. Multivariate analysis of variance (MANOVA) was used to evaluate the differences at a 95% confidence level (p≤0.05). The obtained results show that aqueous solution of ethanol was more appropriate solvent for extraction of phenolic compounds (total flavonoids, total hydroxycinnamic acids and total flavonols) than aqueous solution of methanol. The amount of phenolic compounds was higher in 70% aqueous solution of ethanol or methanol, while higher antioxidant capacity was observed in 50% aqueous solution of methanol. Higher temperature of extraction improved the amount of phenolic compounds and also antioxidant capacity determined by 2,2-diphenyl-1-picrylhydrazyl free radical scavenging capacity assay. Extensive duration of extraction (15- to 25-minute interval) has a significant effect only on the increase of total phenolic content, while specific phenolic compound content and antioxidant capacity were the highest when microwave extraction time of 5 min was applied.
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da Costa César, Isabela; Nogueira, Fernando Henrique Andrade; Pianetti, Gérson Antônio
2008-09-10
This paper describes the development and evaluation of a HPLC, UV spectrophotometry and potentiometric titration methods to quantify lumefantrine in raw materials and tablets. HPLC analyses were carried out using a Symmetry C(18) column and a mobile phase composed of methanol and 0.05% trifluoroacetic acid (80:20), with a flow rate of 1.0ml/min and UV detection at 335nm. For the spectrophotometric analyses, methanol was used as solvent and the wavelength of 335nm was selected for the detection. Non-aqueous titration of lumefantrine was carried out using perchloric acid as titrant and glacial acetic acid/acetic anhydride as solvent. The end point was potentiometrically determined. The three evaluated methods showed to be adequate to quantify lumefantrine in raw materials, while HPLC and UV methods presented the most reliable results for the analyses of tablets.
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Anomalous Protein-Protein Interactions in Multivalent Salt Solution.
Pasquier, Coralie; Vazdar, Mario; Forsman, Jan; Jungwirth, Pavel; Lund, Mikael
2017-04-13
The stability of aqueous protein solutions is strongly affected by multivalent ions, which induce ion-ion correlations beyond the scope of classical mean-field theory. Using all-atom molecular dynamics (MD) and coarse grained Monte Carlo (MC) simulations, we investigate the interaction between a pair of protein molecules in 3:1 electrolyte solution. In agreement with available experimental findings of "reentrant protein condensation", we observe an anomalous trend in the protein-protein potential of mean force with increasing electrolyte concentration in the order: (i) double-layer repulsion, (ii) ion-ion correlation attraction, (iii) overcharge repulsion, and in excess of 1:1 salt, (iv) non Coulombic attraction. To efficiently sample configurational space we explore hybrid continuum solvent models, applicable to many-protein systems, where weakly coupled ions are treated implicitly, while strongly coupled ones are treated explicitly. Good agreement is found with the primitive model of electrolytes, as well as with atomic models of protein and solvent.
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Continuous extraction of organic materials from water
Goldberg, M.C.; DeLong, L.; Kahn, L.
1971-01-01
A continuous liquid solvent extractor, designed to utilize organic solvents that are heavier than water, is described. The extractor is capable of handling input rates up to 2 liters per hour and has a 500-ml. extractant capacity. Extraction efficiency is dependent upon the p-value, the two solvent ratios, rate of flow of the aqueous phase, and rate of reflux of the organic phase. Extractors can be serially coupled to increase extraction efficiency and, when coupled with a lighter-than-water extractor, the system will allow the use of any immiscible solvent.
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Method to produce biomass-derived compounds using a co-solvent system containing gamma-valerolactone
Dumesic, James A.; Motagamwala, Ali Hussain
2017-06-27
A method to produce an aqueous solution of carbohydrates containing C5- and/or C6-sugar-containing oligomers and/or C5- and/or C6-sugar monomers in which biomass or a biomass-derived reactant is reacted with a solvent system having an organic solvent, and organic co-solvent, and water, in the presence of an acid. The method produces the desired product, while a substantial portion of any lignin present in the reactant appears as a precipitate in the product mixture.
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FISSION PRODUCT REMOVAL FROM ORGANIC SOLUTIONS
Moore, R.H.
1960-05-10
The decontamination of organic solvents from fission products and in particular the treatment of solvents that were used for the extraction of uranium and/or plutonium from aqueous acid solutions of neutron-irradiated uranium are treated. The process broadly comprises heating manganese carbonate in air to a temperature of between 300 and 500 deg C whereby manganese dioxide is formed; mixing the manganese dioxide with the fission product-containing organic solvent to be treated whereby the fission products are precipitated on the manganese dioxide; and separating the fission product-containing manganese dioxide from the solvent.
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NASA Astrophysics Data System (ADS)
Mezhevoi, I. N.; Badelin, V. G.; Tyunina, E. Yu.; Kamkina, S. V.
2018-03-01
The integral enthalpies of dissolution of L-tryptophan and L-asparagine in aqueous solutions of sodium dodecyl sulfate (surfactant) at surfactant concentrations of up to 0.05 mol/kg of the solvent are determined and estimated calorimetrically. Standard values of the enthalpies of dissolution and transfer of amino acids from water to a mixed solvent are calculated. The calculated enthalpy coefficients of pair interactions between amino acids and surfactant molecules have positive values. Hydrophobic interactions between amino acids and surfactants have the dominant effect on the enthalpy characteristics of the interaction in a three-component solution.
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NASA Astrophysics Data System (ADS)
Yu, Lei; Han, Mengting; Luan, Jie; Xu, Lin; Ding, Yuanhua; Xu, Qing
2016-07-01
Cheap, abundant but seldom-employed Ca(OH)2 was found to be an excellent low-loading (5-10 mol%) catalyst for Claisen-Schmidt condensation of aldehydes with methyl ketones under mild conditions. It was interesting that dilute aqueous ethanol (20 v/v%) was unexpectedly discovered to be the optimal solvent. The reaction was scalable at least to 100 mmol and calcium could be precipitated by CO2 and removed by filtration. Evaporation of solvent directly afforded the product in the excellent 96% yield with high purity, as confirmed by its 1H NMR spectrum.
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2014-01-01
Background The phenolic contents and antioxidant activities of fruits could be underestimated if the bound phenolic compounds are not considered. In the present study, the extraction efficiencies of various solvents were investigated in terms of the total content of the free and bound phenolic compounds, as well as the phenolic profiles and antioxidant activities of the extracts. Methods Five different solvent mixtures were used to extract the free phenolic compounds from litchi pulp. Alkaline and acidic hydrolysis methods were compared for the hydrolysis of bound phenolic compounds from litchi pulp residue. The phenolic compositions of the free and bound fractions from the litchi pulp were identified using HPLC-DAD. The antioxidant activities of the litchi pulp extracts were determined by oxygen radical absorbance capacity (ORAC) and cellular antioxidant activity (CAA) assays. Results Of the solvents tested, aqueous acetone extracted the largest amount of total free phenolic compounds (210.7 mg GAE/100 g FW) from litchi pulp, followed sequentially by aqueous mixtures of methanol, ethanol and ethyl acetate, and water itself. The acid hydrolysis method released twice as many bound phenolic compounds as the alkaline hydrolysis method. Nine phenolic compounds were detected in the aqueous acetone extract. In contrast, not all of these compounds were found in the other four extracts. The classification and content of the bound phenolic compounds released by the acid hydrolysis method were higher than those achieved by the alkaline hydrolysis. The aqueous acetone extract showing the highest ORAC value (3406.9 μmol TE/100 g FW) for the free phenolic extracts. For the CAA method, however, the aqueous acetone and methanol extracts (56.7 and 55.1 μmol QE/100 g FW) showed the highest levels of activity of the five extracts tested. The ORAC and CAA values of the bound phenolic compounds obtained by acid hydrolysis were 2.6- and 1.9-fold higher than those obtained using the alkaline hydrolysis method. Conclusions The free and bound phenolic contents and profiles and antioxidant activities of the extracts were found to be dependent on the extraction solvent used. Litchi exhibited good cellular antioxidant activity and could be a potentially useful natural source of antioxidants. PMID:24405977
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Synthesis and characterization of oxytetracycline imprinted magnetic polymer for application in food
NASA Astrophysics Data System (ADS)
Aggarwal, Sneha; Rajput, Yudhishthir Singh; Singh, Gulab; Sharma, Rajan
2016-02-01
Magnetic imprinted polymer was prepared by polymerization of methacrylate and ethyleneglycoldimethacrylate in the presence of oxytetracycline on the surface of iron magnetite. Selectivity of prepared polymer was calculated from ratio of partition coefficient of oxytetracycline for imprinted and non- imprinted polymer in water, acetonitrile, methanol and at different pH in aqueous buffer. pH of solvent exhibited pronounced effect on selectivity. Selectivity at pH 7.0, 6.0 and 5.0 was 36.0, 2.25 and 1.61 fold higher than at pH 4.0. Imprinted polymer was not selective for oxytetracycline in methanol. However, selectivity in water and acetonitrile was 19.42 and 2.86, respectively. Oxytetracycline did bind to imprinted polymer in water or aqueous buffer (pH 7.0) and could be eluted with methanol. Prepared polymer extracted 75-80 % oxytetracycline from water, honey and egg white.
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Facile synthesis and photocatalytic activity of bi-phase dispersible Cu-ZnO hybrid nanoparticles
NASA Astrophysics Data System (ADS)
Liu, Xiao; Liu, HongLing; Zhang, WenXing; Li, XueMei; Fang, Ning; Wang, XianHong; Wu, JunHua
2015-04-01
Bi-phase dispersible Cu-ZnO hybrid nanoparticles were synthesized by one-pot non-aqueous nanoemulsion with the use of poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) (PEO-PPO-PEO) as the surfactant. The transmission electron microscopy (TEM) and X-ray diffraction (XRD) show high crystallinity of the Cu-ZnO hybrid nanoparticles and an average particle size of ~19.4 nm. The ultraviolet-visible light absorbance spectrometry (UV-vis) and photoluminescence spectrophotometry (PL) demonstrate well dispersibility and excellent optical performance of Cu-ZnO hybrid nanoparticles both in organic and aqueous solvent. The X-ray photoelectron spectroscopy (XPS) confirms Cu1+ and Cu2+ in ZnO. The observation using Sudan red (III) as probe molecule reveals that the Cu-ZnO hybrid nanoparticles possess enhanced photocatalytic activity and stability which are promising for potential applications in photocatalysis.
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Toxicity of medicinal plants used in traditional medicine in Northern Peru
Bussmann, R.W.; Malca, G.; Glenn, A.; Sharon, D.; Nilsen, B.; Parris, B.; Dubose, D; Ruiz, D.; Saleda, J.; Martinez, M.; Carillo, L.; Walker, K.; Kuhlman, A.; Townesmith, A.
2011-01-01
Aim The plant species reported here are traditionally used in Northern Peru for a wide range of illnesses. Most remedies are prepared as ethanol or aqueous extracts and then ingested. The aim of this study was to evaluate the potential toxicity of these extracts. Materials and methods The toxicity of ethanolic and water extracts of 341 plant species was determined using a Brine-Shrimp assay. Results Overall 24% of the species in water extract and 76% of the species in alcoholic extract showed elevated toxicity levels to brine-shrimp. Although in most cases multiple extracts of the same species showed very similar toxicity values, in some cases the toxicity of different extracts of the same species varied from non-toxic to highly toxic. Conclusions Traditional preparation methods take different toxicity levels in aqueous and ethanol extracts into account when choosing the appropriate solvent for the preparation of a remedy. PMID:21575699
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Applying green chemistry to the photochemical route to artemisinin
NASA Astrophysics Data System (ADS)
Amara, Zacharias; Bellamy, Jessica F. B.; Horvath, Raphael; Miller, Samuel J.; Beeby, Andrew; Burgard, Andreas; Rossen, Kai; Poliakoff, Martyn; George, Michael W.
2015-06-01
Artemisinin is an important antimalarial drug, but, at present, the environmental and economic costs of its semi-synthetic production are relatively high. Most of these costs lie in the final chemical steps, which follow a complex acid- and photo-catalysed route with oxygenation by both singlet and triplet oxygen. We demonstrate that applying the principles of green chemistry can lead to innovative strategies that avoid many of the problems in current photochemical processes. The first strategy combines the use of liquid CO2 as solvent and a dual-function solid acid/photocatalyst. The second strategy is an ambient-temperature reaction in aqueous mixtures of organic solvents, where the only inputs are dihydroartemisinic acid, O2 and light, and the output is pure, crystalline artemisinin. Everything else—solvents, photocatalyst and aqueous acid—can be recycled. Some aspects developed here through green chemistry are likely to have wider application in photochemistry and other reactions.
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Applying green chemistry to the photochemical route to artemisinin.
Amara, Zacharias; Bellamy, Jessica F B; Horvath, Raphael; Miller, Samuel J; Beeby, Andrew; Burgard, Andreas; Rossen, Kai; Poliakoff, Martyn; George, Michael W
2015-06-01
Artemisinin is an important antimalarial drug, but, at present, the environmental and economic costs of its semi-synthetic production are relatively high. Most of these costs lie in the final chemical steps, which follow a complex acid- and photo-catalysed route with oxygenation by both singlet and triplet oxygen. We demonstrate that applying the principles of green chemistry can lead to innovative strategies that avoid many of the problems in current photochemical processes. The first strategy combines the use of liquid CO2 as solvent and a dual-function solid acid/photocatalyst. The second strategy is an ambient-temperature reaction in aqueous mixtures of organic solvents, where the only inputs are dihydroartemisinic acid, O2 and light, and the output is pure, crystalline artemisinin. Everything else-solvents, photocatalyst and aqueous acid-can be recycled. Some aspects developed here through green chemistry are likely to have wider application in photochemistry and other reactions.
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Solvent Dependent Disorder in M 2(BzOip) 2(H 2O)·Solvate (M = Co or Zn)
McCormick, Laura; Morris, Samuel A.; Teat, Simon J.; ...
2017-12-24
Coordination polymers derived from 5-benzyloxy isophthalic acid (H 2BzOip) are rare, with only three reported that do not contain additional bridging ligands, of which two M 2(BzOip) 2(H 2O) (M = Co and Zn) are isomorphous. It was hoped that by varying the solvent system in a reaction between H 2BzOip and M(OAc) 2 (M = Co and Zn), from water to a water/alcohol mixture, coordination polymers of different topology could be formed. Instead, two polymorphs of the existing M 2(BzOip) 2(H 2O) (M = Co and Zn) were isolated from aqueous methanol and aqueous ethanol, in which a smallmore » number of guest solvent molecules are present in the crystals. These guest water molecules disrupt the hexaphenyl embrace motif, leading to varying degrees of disorder of the benzyl groups.« less
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Vasileiou, Kalliopi; Vysloužil, Jakub; Pavelková, Miroslava; Vysloužil, Jan; Kubová, Kateřina
2018-01-01
Size-reduced microparticles were successfully obtained by solvent evaporation method. Different parameters were applied in each sample and their influence on microparticles was evaluated. As a model drug the insoluble ibuprofen was selected for the encapsulation process with Eudragit® RS. The obtained microparticles were inspected by optical microscopy and scanning electron microscopy. The effect of aqueous phase volume (600, 400, 200 ml) and the concentration of polyvinyl alcohol (PVA; 1.0% and 0.1%) were studied. It was evaluated how those variations and also size can affect microparticle characteristics such as encapsulation efficiency, drug loading, burst effect and microparticle morphology. It was observed that the sample prepared with 600 ml aqueous phase and 1% concentration of polyvinyl alcohol gave the most favorable results.Key words: microparticles solvent evaporation sustained drug release Eudragit RS®.
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Solvent Dependent Disorder in M 2(BzOip) 2(H 2O)·Solvate (M = Co or Zn)
DOE Office of Scientific and Technical Information (OSTI.GOV)
McCormick, Laura; Morris, Samuel A.; Teat, Simon J.
Coordination polymers derived from 5-benzyloxy isophthalic acid (H 2BzOip) are rare, with only three reported that do not contain additional bridging ligands, of which two M 2(BzOip) 2(H 2O) (M = Co and Zn) are isomorphous. It was hoped that by varying the solvent system in a reaction between H 2BzOip and M(OAc) 2 (M = Co and Zn), from water to a water/alcohol mixture, coordination polymers of different topology could be formed. Instead, two polymorphs of the existing M 2(BzOip) 2(H 2O) (M = Co and Zn) were isolated from aqueous methanol and aqueous ethanol, in which a smallmore » number of guest solvent molecules are present in the crystals. These guest water molecules disrupt the hexaphenyl embrace motif, leading to varying degrees of disorder of the benzyl groups.« less
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Chum, H.L.; Black, S.K.; Diebold, J.P.; Kreibich, R.E.
1993-06-29
A process is described for preparing phenol-formaldehyde novolak resins and molding compositions in which portions of the phenol normally contained in said resins are replaced by a phenol/neutral fractions extract obtained from fractionating fast-pyrolysis oils. The fractionation consists of a neutralization stage which can be carried out with aqueous solutions of bases or appropriate bases in the dry state, followed by solvent extraction with an organic solvent having at least a moderate solubility parameter and good hydrogen bonding capacity. Phenolic compounds-containing/neutral fractions extracts obtained by fractionating fast-pyrolysis oils from a lignocellulosic material, is such that the oil is initially in the pH range of 2-4, being neutralized with an aqueous bicarbonate base, and extracted into a solvent having a solubility parameter of approximately 8.4-9.11 [cal/cm[sup 3
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The Determination of Lead in Gasoline by Atomic Absorption Spectrometry.
ERIC Educational Resources Information Center
Coleman, M. F. M.
1985-01-01
Describes an experiment that involves the extraction of lead from gasoline into an aqueous solvent using iodine monochloride reagent. This method (which avoids the aspiration of organic solvents) also illustrates the use of wavelengths other than the most sensitive wavelength and effects of flame stoichiometry and burner height upon absorbance.…
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Sorbent and solvent characteristics influencing sorption of pentachlorophenol (PCP) were investigated. Analysis of aqueous sorption data for several sorbents over a broad pH range suggested hydrophobic sorption of neutral PCP predominates at pH 7. At pH > 7, sorption of the penta...
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Hemin-utilizing G-quadruplex DNAzymes are strongly active in organic co-solvents.
Canale, Thomas D; Sen, Dipankar
2017-05-01
The widespread use of organic solvents in industrial processes has focused in recent years on the utility of "green" solvents - those with less harmful environmental, health, and safety properties - such as methanol and formamide. However, protein enzymes, regarded as green catalysts, are often incompatible with organic solvents. Herein, we have explored the oxidative properties of a Fe(III)-heme, or hemin, utilizing catalytic DNA (heme·DNAzyme) in different green solvent-water mixtures. We find that the peroxidase and peroxygenase activities of the heme·DNAzyme are strongly enhanced in 20-30% v/v methanol or formamide, relative to water alone. Protic solvent content of >30% v/v gradually diminishes heme·DNAzyme catalytic activity; however, the heme·DNAzyme is still active in as high as 80% v/v methanol. In contrast to protic solvents, aqueous dimethylformamide solutions largely inhibit heme·DNAzyme activity. In view of the strong catalytic activity of heme·DNAzyme in aqueous methanol, we were able to determine that a 60% v/v methanol-water mixture gives the most optimal yield of the dibenzothiophene sulfoxide (DBTO) oxidation product of petroleum-derived dibenzothiophene (DBT). The high product yield reflects both DNAzyme catalysis and a high substrate availability. Overall, these results emphasize the excellent promise of G-quadruplex forming DNA catalysts in application to "greener" industrial chemistry. This article is part of a Special Issue entitled "G-quadruplex" Guest Editor: Dr. Concetta Giancola and Dr. Daniela Montesarchio. Copyright © 2016 Elsevier B.V. All rights reserved.
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Lannan, Ford M; Mamajanov, Irena; Hud, Nicholas V
2012-09-19
Structures formed by human telomere sequence (HTS) DNA are of interest due to the implication of telomeres in the aging process and cancer. We present studies of HTS DNA folding in an anhydrous, high viscosity deep eutectic solvent (DES) comprised of choline choride and urea. In this solvent, the HTS DNA forms a G-quadruplex with the parallel-stranded ("propeller") fold, consistent with observations that reduced water activity favors the parallel fold, whereas alternative folds are favored at high water activity. Surprisingly, adoption of the parallel structure by HTS DNA in the DES, after thermal denaturation and quick cooling to room temperature, requires several months, as opposed to less than 2 min in an aqueous solution. This extended folding time in the DES is, in part, due to HTS DNA becoming kinetically trapped in a folded state that is apparently not accessed in lower viscosity solvents. A comparison of times required for the G-quadruplex to convert from its aqueous-preferred folded state to its parallel fold also reveals a dependence on solvent viscosity that is consistent with Kramers rate theory, which predicts that diffusion-controlled transitions will slow proportionally with solvent friction. These results provide an enhanced view of a G-quadruplex folding funnel and highlight the necessity to consider solvent viscosity in studies of G-quadruplex formation in vitro and in vivo. Additionally, the solvents and analyses presented here should prove valuable for understanding the folding of many other nucleic acids and potentially have applications in DNA-based nanotechnology where time-dependent structures are desired.
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NASA Astrophysics Data System (ADS)
Mezhevoi, I. N.; Badelin, V. G.
2015-03-01
Integral enthalpies of dissolution Δsol H m of L-cysteine, L-serine, and L-asparagine in aqueous solutions of 1,3-propylene glycol at organic solvent concentrations of up to 0.26 mole fraction are measured via the thermochemistry of dissolution. Standard enthalpies of dissolution (Δsol H ○) and transfer (Δtr H ○) of amino acids from water to a mixed solvent are calculated. It is found that the calculated enthalpy coefficients of pair interactions of the amino acids with polyhydric alcohol molecules have positive values. The effect the arrangement of the hydroxyl group in the structure of polyhydric alcohols has on the enthalpy of interaction of amino acids in aqueous solutions is revealed. The effect of different types of interactions in solutions and the structural features of biomolecules and cosolvents on the enthalpy of dissolution of amino acids is analyzed.
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NASA Astrophysics Data System (ADS)
Zhang, Xian-Rui; Zhang, Lei
2017-06-01
Three salt solvates of azilsartan (AZ) with 2-methylimidazole (2MI) (namely AZ-2MI-H2O, AZ-2MI-ACE and AZ-2MI-THF) and one azilsartan solvate (AZ-DIO, ACE = acetone, THF = tetrahydrofuran, and DIO = 1,4-dioxane) were manufactured by solvent-controlled self-assembly in aqueous-organic solutions. The experimental result of AZ-DIO shows that AZ is high affinity to DIO molecule, which has a unique ability to prevent salt formation between AZ and 2MI. Thermal studies of three salt solvates exhibit poor thermodynamic stability in environmental conditions. Solubility experiments show that AZ-2MI-ACE and AZ-2MI-THF are unstable and convert to AZ-2MI-H2O in aqueous solution, and that AZ-2MI-H2O exhibits increased solubility and retention stability in an aqueous medium compared with the commercial AZ-A crystalline form.
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EXTRACTION OF URANYL NITRATE FROM AQUEOUS SOLUTIONS
Furman, N.H.; Mundy, R.J.
1957-12-10
An improvement in the process is described for extracting aqueous uranyl nitrate solutions with an organic solvent such as ether. It has been found that the organic phase will extract a larger quantity of uranyl nitrate if the aqueous phase contains in addition to the uranyl nitrate, a quantity of some other soluble nitrate to act as a salting out agent. Mentioned as suitable are the nitrates of lithium, calcium, zinc, bivalent copper, and trivalent iron.
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NASA Astrophysics Data System (ADS)
Le, Thom; Cao, Diem Kieu; Pham, Thanh Vy; Huynh, Tan Dat; Ta, Nhat Thuy Anh; Nguyen, Ngoc Thao Linh; Nguyen, Huu Thanh; Le, Hue Huong; Bui, Anh Vo; Truong, Dieu-Hien
2018-04-01
Callisia fragrans is a wonder herb with many medicinal properties such as burn, dental diseases, cancer diseases and arthritis in folk medicine. It is noted that the phytochemical constituents and antimicrobial activity of traditional plants depend on not only the extracting method but also the solvent used for extraction. In this study, the effect of five extraction solvents (i.e., distilled water, 80% methanol, 80% ethanol, 80% ethyl acetate, and 80% chloroform) on yield, total phenolic content (TPC) and total flavonoid content (TFC) of Callisia leaves was determined. Besides, changes in anti-Lactobacillus fermentum activity of C. fragrans freeze-dried extract was also evaluated using disk-diffusion method. The recovery percentage of extractable yield of fresh leaves are ranged from 11.93% w/w for distilled water extract to 16.60% w/w for aqueous ethanol extracts. The yield of 80% aqueous methanol extract (16.27% w/w) is only slightly less than that of the ethanol extract. Significant differences were observed among TPC and TFC obtaining by 80% methanol (0.0522% and 0.0335% w/w, respectively) compared to other solvents (p < 0.05). TPC and TFC of C. fragrans extracts increase in the following order: distilled water < 80% chloroform < 80% ethyl acetate < 80% ethanol < 80% methanol. The results revealed that 80% aqueous methanol Calissia extracts has moderate inhibition (9.0 mm of inhibition zone for 1.5 mg/mL of extracts) of L. fermentum compared to standard antibacterial agent. Based on the study results, it can be concluded that the yield, TPC and TFC of C. frgrans extract varied with the extracting solvent. It also showed that Callisia extracts can prevent dental caries by inhibiting the growth of L. fermentum, towards new insights for treatment of dental caries.
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Hisamatsu, Yosuke; Miyazawa, Yuya; Yoneda, Kakeru; Miyauchi, Miki; Zulkefeli, Mohd; Aoki, Shin
2016-01-01
We previously reported on supramolecular complexes 4 and 5, formed by the 4 : 4 : 4 or 2 : 2 : 2 assembly of a dimeric zinc(II) complex (Zn2L(1)) having 2,2'-bipyridyl linker, dianion of cyanuric acid (CA) or 5,5-diethylbarbituric acid (Bar), and copper(II) ion (Cu(2+)) in an aqueous solution. The supermolecule 4 possesses Cu2(μ-OH)2 centers and catalyzes hydrolysis of phosphate monoester dianion, mono(4-nitrophenyl)phosphate (MNP), at neutral pH. In this manuscript, we report on design and synthesis of hydrophobic supermolecules 9 and 10 by 4 : 4 : 4 and 2 : 2 : 2 self-assembly of hydrophobic Zn2L(2) and Zn2L(3) containing long alkyl chains, CA or Bar, and Cu(2+) and their phosphatase activity for the hydrolysis of MNP and bis(4-nitrophenyl)phosphate (BNP) in two-phase solvent systems. We assumed that the Cu2(μ-OH)2 active sites of 9 and 10 would be more stable in organic solvent than in aqueous solution and that product inhibition of the supermolecules might be avoided by the release of HPO4(2-) into the aqueous layer. The findings indicate that 9 and 10 exhibit phosphatase activity in the two-phase solvent system, although catalytic turnover was not observed. Furthermore, the hydrolysis of BNP catalyzed by the hydrophobic 2 : 2 : 2 supermolecules in the two-phase solvent system is described.
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Vijaya Saradhi, U V R; Prabhakar, S; Jagadeshwar Reddy, T; Murty, M R V S
2007-07-20
In the present paper, we report an improved ion-pair solid-phase extraction (IP-SPE) method for the analysis of alkylphosphonic acids, namely, methyl, ethyl and propylphosphonic acids, present in the aqueous sample. The aqueous sample was mixed with an ion-pair reagent, phenyltrimethylammonium hydroxide (PTMAH) and passed through activated charcoal SPE cartridge. The retained chemicals in the cartridge were extracted with methanol and analysed by gas chromatography-mass spectrometry (GC-MS) under the electron impact ionization (EI) mode. The analytes were converted to their methyl esters by pyrolytic methylation in the hot GC injection port. The recoveries of alkylphosphonic acids were above 95% and the minimum detection limits were as low as 10 ng/mL. The recovery of the test chemicals was tested with solvents, dichloromethane, n-hexane, ethyl acetate, acetone, acetonitrile and methanol. The chemicals could be efficiently extracted by the hydrophilic solvents. The method did not work at the highly acidic pH (when acidified with dilute HCl) but worked well from pH 4.0 to 14.0. The present method was also tested with other tetra-(methyl, ethyl, propyl and n-butyl)ammonium hydroxides. The test chemicals were not converted to their methyl and ethyl esters with tetramethyl and tetraethylammonium hydroxides, whereas they were converted to their corresponding propyl and n-butyl esters with tetrapropyl and tetra(n-butyl)ammonium hydroxides. The method was also applied to two highly cross-linked polymeric sorbents DSC-6S and Oasis HLB. The recovery of the chemicals on these sorbents was observed to be poor. Methylation using phenyltrimethylammonium hydroxide is non-hazardous and advantageous over methylation using diazomethane. The method was applied to the analysis of aqueous samples given in one of the official proficiency tests conducted by the Organization for the Prohibition of Chemical Weapons and all the spiked chemicals were identified as methyl esters.
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NASA Astrophysics Data System (ADS)
Sun, Hui; Wen, Jiayi; Zhao, Yanxiang; Li, Bo; McCammon, J. Andrew
2015-12-01
Dielectric boundary based implicit-solvent models provide efficient descriptions of coarse-grained effects, particularly the electrostatic effect, of aqueous solvent. Recent years have seen the initial success of a new such model, variational implicit-solvent model (VISM) [Dzubiella, Swanson, and McCammon Phys. Rev. Lett. 96, 087802 (2006) and J. Chem. Phys. 124, 084905 (2006)], in capturing multiple dry and wet hydration states, describing the subtle electrostatic effect in hydrophobic interactions, and providing qualitatively good estimates of solvation free energies. Here, we develop a phase-field VISM to the solvation of charged molecules in aqueous solvent to include more flexibility. In this approach, a stable equilibrium molecular system is described by a phase field that takes one constant value in the solute region and a different constant value in the solvent region, and smoothly changes its value on a thin transition layer representing a smeared solute-solvent interface or dielectric boundary. Such a phase field minimizes an effective solvation free-energy functional that consists of the solute-solvent interfacial energy, solute-solvent van der Waals interaction energy, and electrostatic free energy described by the Poisson-Boltzmann theory. We apply our model and methods to the solvation of single ions, two parallel plates, and protein complexes BphC and p53/MDM2 to demonstrate the capability and efficiency of our approach at different levels. With a diffuse dielectric boundary, our new approach can describe the dielectric asymmetry in the solute-solvent interfacial region. Our theory is developed based on rigorous mathematical studies and is also connected to the Lum-Chandler-Weeks theory (1999). We discuss these connections and possible extensions of our theory and methods.
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Sun, Hui; Wen, Jiayi; Zhao, Yanxiang; Li, Bo; McCammon, J Andrew
2015-12-28
Dielectric boundary based implicit-solvent models provide efficient descriptions of coarse-grained effects, particularly the electrostatic effect, of aqueous solvent. Recent years have seen the initial success of a new such model, variational implicit-solvent model (VISM) [Dzubiella, Swanson, and McCammon Phys. Rev. Lett. 96, 087802 (2006) and J. Chem. Phys. 124, 084905 (2006)], in capturing multiple dry and wet hydration states, describing the subtle electrostatic effect in hydrophobic interactions, and providing qualitatively good estimates of solvation free energies. Here, we develop a phase-field VISM to the solvation of charged molecules in aqueous solvent to include more flexibility. In this approach, a stable equilibrium molecular system is described by a phase field that takes one constant value in the solute region and a different constant value in the solvent region, and smoothly changes its value on a thin transition layer representing a smeared solute-solvent interface or dielectric boundary. Such a phase field minimizes an effective solvation free-energy functional that consists of the solute-solvent interfacial energy, solute-solvent van der Waals interaction energy, and electrostatic free energy described by the Poisson-Boltzmann theory. We apply our model and methods to the solvation of single ions, two parallel plates, and protein complexes BphC and p53/MDM2 to demonstrate the capability and efficiency of our approach at different levels. With a diffuse dielectric boundary, our new approach can describe the dielectric asymmetry in the solute-solvent interfacial region. Our theory is developed based on rigorous mathematical studies and is also connected to the Lum-Chandler-Weeks theory (1999). We discuss these connections and possible extensions of our theory and methods.
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Sun, Hui; Wen, Jiayi; Zhao, Yanxiang; Li, Bo; McCammon, J. Andrew
2015-01-01
Dielectric boundary based implicit-solvent models provide efficient descriptions of coarse-grained effects, particularly the electrostatic effect, of aqueous solvent. Recent years have seen the initial success of a new such model, variational implicit-solvent model (VISM) [Dzubiella, Swanson, and McCammon Phys. Rev. Lett. 96, 087802 (2006) and J. Chem. Phys. 124, 084905 (2006)], in capturing multiple dry and wet hydration states, describing the subtle electrostatic effect in hydrophobic interactions, and providing qualitatively good estimates of solvation free energies. Here, we develop a phase-field VISM to the solvation of charged molecules in aqueous solvent to include more flexibility. In this approach, a stable equilibrium molecular system is described by a phase field that takes one constant value in the solute region and a different constant value in the solvent region, and smoothly changes its value on a thin transition layer representing a smeared solute-solvent interface or dielectric boundary. Such a phase field minimizes an effective solvation free-energy functional that consists of the solute-solvent interfacial energy, solute-solvent van der Waals interaction energy, and electrostatic free energy described by the Poisson–Boltzmann theory. We apply our model and methods to the solvation of single ions, two parallel plates, and protein complexes BphC and p53/MDM2 to demonstrate the capability and efficiency of our approach at different levels. With a diffuse dielectric boundary, our new approach can describe the dielectric asymmetry in the solute-solvent interfacial region. Our theory is developed based on rigorous mathematical studies and is also connected to the Lum–Chandler–Weeks theory (1999). We discuss these connections and possible extensions of our theory and methods. PMID:26723595
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URANIUM DECONTAMINATION WITH RESPECT TO ZIRCONIUM
Vogler, S.; Beederman, M.
1961-05-01
A process is given for separating uranium values from a nitric acid aqueous solution containing uranyl values, zirconium values and tetravalent plutonium values. The process comprises contacting said solution with a substantially water-immiscible liquid organic solvent containing alkyl phosphate, separating an organic extract phase containing the uranium, zirconium, and tetravalent plutonium values from an aqueous raffinate, contacting said organic extract phase with an aqueous solution 2M to 7M in nitric acid and also containing an oxalate ion-containing substance, and separating a uranium- containing organic raffinate from aqueous zirconium- and plutonium-containing extract phase.
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Van Winkle, Q.; Kraus, K.A.
1959-10-27
A process is presented for separating polonium, protactinium, or mixtures thereof in aqueous solution from bismuth, zirconium, lead, and niobium values contained in the solution. The method comprises providing hydrochloric acid in the solution in a concentration of at least 5N. contacting the aqueous solution with a substantially waterimmiscible organic solvent such as diisopropyl ketone, and separating the aqueous phase containing the bismuth, zirconium, lead, and niobium from the organic extract phase containing the polonium, protactinium, or mixture thereof.
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Moyo, Francis; Tandlich, Roman; Wilhelmi, Brendan S.; Balaz, Stefan
2014-01-01
Renewed focus on the sorption of hydrophobic organic chemicals (HOCs) onto mineral surfaces and soil components is required due to the increased and wider range of organic pollutants being released into the environment. This mini-review examines the possibility of the contribution and mechanism of HOC sorption onto clay mineral sorbents such as kaolinite, and soil organic matter and the possible role of both in the prevention of environmental contamination by HOCs. Literature data indicates that certain siloxane surfaces can be hydrophobic. Therefore soils can retain HOCs even at low soil organic levels and the extent will depend on the structure of the pollutant and the type and concentration of clay minerals in the sorbent. Clay minerals are wettable by nonpolar solvents and so sorption of HOCs onto them from aqueous and non-aqueous solutions is possible. This is important for two reasons: firstly, the movement and remediation of soil environments will be a function of the concentration and type of clay minerals in the soil. Secondly, low-cost sorbents such as kaolinite and expandable clays can be added to soils or contaminated environments as temporary retention barriers for HOCs. Inorganic cations sorbed onto the kaolinite have a strong influence on the rate and extent of sorption of hydrophobic organic pollutants onto kaolinite. Structural sorbate classes that can be retained by the kaolinite matrix are limited by hydrogen bonding between hydroxyl groups of the octahedral alumosilicate sheet and the tetrahedral sheet with silicon. Soil organic carbon plays a key role in the sorption of HOCs onto soils, but the extent will be strongly affected by the structure of the organic soil matter and the presence of soot. Structural characterisation of soil organic matter in a particular soil should be conducted during a particular contamination event. Contamination by mining extractants and antibiotics will require renewed focus on the use of the QSAR approaches in the context of the sorption of HOCs onto clay minerals from aqueous and non-aqueous solutions. PMID:24821385
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Heteroatom incorporated coke for electrochemical cell electrode
Lewis, Irwin Charles; Greinke, Ronald Alfred
1997-01-01
This invention relates to an electrode for a coke/alkali metal electrochemical cell comprising: (a) calcined coke particles: (i) that contain at least 0.5 weight percent of nitrogen heteroatoms and at least 1.0 weight percent sulfur heteroatoms, and (ii) that have an average particle size from 2 microns to 40 microns with essentially no particles being greater than 50 microns. (b) a binder This invention also relates to a coke/alkali metal electrochemical cell comprising: (a) an electrode as described above, (b) a non-aqueous electrolytic solution comprising an organic aprotic solvent and an electrically conductive salt, and (c) a counterelectrode.
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Long life lithium batteries with stabilized electrodes
Amine, Khalil [Downers Grove, IL; Liu, Jun [Naperville, IL; Vissers, Donald R [Naperville, IL; Lu, Wenquan [Darien, IL
2009-03-24
The present invention relates to non-aqueous electrolytes having electrode stabilizing additives, stabilized electrodes, and electrochemical devices containing the same. Thus the present invention provides electrolytes containing an alkali metal salt, a polar aprotic solvent, and an electrode stabilizing additive. In some embodiments the additives include a substituted or unsubstituted cyclic or spirocyclic hydrocarbon containing at least one oxygen atom and at least one alkenyl or alkynyl group. When used in electrochemical devices with, e.g., lithium manganese oxide spinel electrodes or olivine or carbon-coated olivine electrodes, the new electrolytes provide batteries with improved calendar and cycle life.
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Gurram, Rajesh Kumar; Gandra, Suchithra; Shastri, Nalini R
2016-03-10
The objective of the study was to design and optimize a disintegrating pellet formulation of microcrystalline cellulose by non-aqueous extrusion process for a water sensitive drug using various statistical tools. Aspirin was used as a model drug. Disintegrating matrix pellets of aspirin using propylene glycol as a non-aqueous granulation liquid and croscarmellose as a disintegrant was developed. Plackett-Burman design was initially conducted to screen and identify the significant factors. Final optimization of formula was performed by response surface methodology using a central composite design. The critical attributes of the pellet dosage forms (dependent variables); disintegration time, sphericity and yield were predicted with adequate accuracy based on the regression model. Pareto charts and contour charts were studied to understand the influence of factors and predict the responses. A design space was constructed to meet the desirable targets of the responses in terms of disintegration time <5min, maximum yield, sphericity >0.95 and friability <1.7%. The optimized matrix pellets were enteric coated using Eudragit L 100. The drug release from the enteric coated pellets after 30min in the basic media was ~93% when compared to ~77% from the marketed pellets. The delayed release pellets stored at 25°C/60% RH were stable for a period of 10mo. In conclusion, it can be stated that the developed process for disintegrating pellets using non-aqueous granulating agents can be used as an alternative technique for various water sensitive drugs, circumventing the application of volatile organic solvents in conventional drug layering on inert cores. The scope of this study can be further extended to hydrophobic drugs, which may benefit from the rapid disintegration property and the use of various hydrophilic excipients used in the optimized pellet formulation to enhance dissolution and in turn improve bioavailability. Copyright © 2016 Elsevier B.V. All rights reserved.
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How to examine soil sorption of ionizable organic compounds and avoid varying pH?
NASA Astrophysics Data System (ADS)
Borisover, Mikhail
2017-04-01
Multiple natural and anthropogenic organic compounds including new and emerging pollutants undergo ionization in aqueous solutions, and their sorption by soils and sediments is contributed by presence of both molecular and ionized species. Better understanding of environmental fate of organic chemicals requires taking into account interactions of molecular and ionized species with environmental sorbents. A "standard" (and undoubtedly important) procedure for differentiating contributions of molecular and ionized species into the overall soil sorption of an organic compound involves varying pH of solution in batch sorption experiments. However, varying pH is (1) often not possible, without destroying a sorbent, e.g., due to the buffer capacity of soils containing carbonates, (2) difficult for further interpretation, since it changes not only the ionization status of a solute in a solution but also the sorbent structure, e.g., a conformation of organic matter, and/or ionization of surface functional groups, (3) making difficult (or even impossible) to explicitly evaluate the role of dissolved species-bulk water interactions, directly affecting the affinity of a sorbate to distribute between water and a sorbent. Indeed, both molecular and ionized species undergo interactions with the solvent bulk and, at least in the case of the ionized ones, there was no a simple way to quantify organic ion-water interactions and their role in organic ion distribution between soil and water phases. This paper presents a "counter-intuitive" approach to examine sorption interactions of an ionizable compound, without experimenting with varied pH. The approach is based on an idea of replacing an initial state in sorption transfer of an ionizable compound from the solvent bulk to a solvated (hydrated) sorbed state: a traditional coefficient describing distribution of a partially ionized compound between a hydrated sorbent and a co-equilibrated aqueous phase is converted to the coefficient describing the transfer of the sorbing compound from its initial molecular (non-ionized) state (in a solution or in the gas phase) to the final hydrated sorbed state equilibrated with the actual aqueous solution of this ionizable compound. In this way, any contributions from the bulk solvent-organic ion interactions into the sorption transfer may be excluded; in addition, further any solute-solvent interactions may be taken out of the consideration. Therefore, compound's sorption characteristics "cleared" of solute-solvent interactions may be obtained, and a better understanding of relations between interactions in a sorbed phase and a molecular structure of organic sorbates can be reached. The approach is illustrated by examining sorption of variously ionized organic compounds, i.e., those belonging to the pharmaceuticals and personal care products (triclosan, gemfibrozil, galaxolide), and aliphatic organic acids on natural and organic amendment-enriched soils. Specifically, it is demonstrated how the greater H-donating ability of trifluoroacetic acid, as compared with acetic acid, strengthens the acid interactions in the soil phase. In another series of examples, it is shown how hydrophobic and non-ionizing galaxolide interacts weakly with soils, as compared with partially ionized triclosan and almost fully ionized gemfibrozil, i.e., leading to the conclusions not reachable based only on the direct comparison of experimentally measured distribution coefficients.
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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
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Hunter, Howard N.; Demcoe, A. Ross; Jenssen, Håvard; Gutteberg, Tore J.; Vogel, Hans J.
2005-01-01
Lactoferricins are highly basic bioactive peptides that are released in the stomach through proteolytic cleavage of various lactoferrin proteins. Here we have determined the solution structure of human lactoferricin (LfcinH) by conventional two-dimensional nuclear magnetic resonance methods in both aqueous solution and a membrane mimetic solvent. Unlike the 25-residue bovine lactoferricin (LfcinB), which adopts a somewhat distorted antiparallel β sheet, the longer LfcinH peptide shows a helical content from Gln14 to Lys29 in the membrane mimetic solvent but a nonexistent β-sheet character in either the N- or C-terminal regions of the peptide. The helical characteristic of the LfcinH peptide resembles the conformation that this region adopts in the crystal structure of the intact protein. The LfcinH structure determined in aqueous solution displays a nascent helix in the form of a coiled conformation in the region from Gln14 to Lys29. Numerous hydrophobic interactions create the basis for the better-defined overall structure observed in the membrane mimetic solvent. The 49-residue LfcinH peptide isolated for these studies was found to be slightly longer than previously reported peptide preparations and was found to have an intact peptide bond between residues Ala11 and Val12. The distinct solution structures of LfcinH and LfcinB represent a novel difference in the physical properties of these two peptides, which contributes to their unique physiological activities. PMID:16048952
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Ward, Keeran; Stuckey, David C
2016-06-01
Refractive index matching was used to create optically transparent polyaphrons to enable proteins adsorbed to the aphron surface to be characterized. Due to the significant light scattering created by polyaphrons, refractive index matching allowed for representative circular dichroism (CD) spectra and acceptable structural characterization. The method utilized n-hexane as the solvent phase, a mixture of glycerol and phosphate buffer (30% [w/v]) as the aqueous phase, and the non-ionic surfactants, Laureth-4 and Kolliphor P-188. Deconvolution of CD spectra revealed that the immobilized protein adapted its native conformation, showing that the adsorbed protein interacted only with the bound water layer ("soapy shell") of the aphron. Isothermal calorimetry further demonstrated that non-ionic surfactant interactions were virtually non-existent, even at the high concentrations used (5% [w/v]), proving that non-ionic surfactants can preserve protein conformation. Copyright © 2016 Elsevier B.V. All rights reserved.
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Investigations of oxygen reduction reactions in non-aqueous electrolytes and the lithium-air battery
NASA Astrophysics Data System (ADS)
O'Laoire, Cormac Micheal
Unlocking the true energy capabilities of the lithium metal negative electrode in a lithium battery has until now been limited by the low capacity intercalation and conversion reactions at the positive electrodes. This is overcome by removing these electrodes and allowing lithium to react directly with oxygen in the atmosphere forming the Li-air battery. Chapter 2 discusses the intimate role of electrolyte, in particular the role of ion conducting salts on the mechanism and kinetics of oxygen reduction in non-aqueous electrolytes designed for such applications and in determining the reversibility of the electrode reactions. Such fundamental understanding of this high energy density battery is crucial to harnessing its full energy potential. The kinetics and mechanisms of O2 reduction in solutions of hexafluorophosphate salts of the general formula X+ PF6-, where, X = tetra butyl ammonium (TBA), K, Na and Li, in acetonitrile have been studied on glassy carbon electrodes using cyclic voltammetry (CV) and rotating disk electrode (RDE) techniques. Our results show that cation choice strongly influences the reduction mechanism of O2. Electrochemical data supports the view that alkali metal oxides formed via electrochemical and chemical reactions passivate the electrode surface inhibiting the kinetics and reversibility of the processes. The O2 reduction mechanisms in the presence of the different cations have been supplemented by kinetic parameters determined from detailed analyses of the CV and RDE data. The organic solvent present in the Li+-conducting electrolyte has a major role on the reversibility of each of the O2 reduction products as found from the work discussed in the next chapter. A fundamental study of the influence of solvents on the oxygen reduction reaction (ORR) in a variety of non-aqueous electrolytes was conducted in chapter 4. In this work special attention was paid to elucidate the mechanism of the oxygen electrode processes in the rechargeable Li-air battery. Towards this end, using either tetrabutylammonium hexafluorophosphate (TBAPF6) or lithium hexafluorophosphate (LiPF6) electrolyte solutions in four different solvents, namely, dimethyl sulfoxide (DMSO), acetonitrile (MeCN), dimethoxyethane (DME), and tetraethylene glycol dimethyl ether (TEGDME), possessing a range of properties, we have determined that the solvent and the supporting electrolyte cations in the solution act in concert to influence the nature of reduction products and their rechargeability. In solutions containing TBA +, O2 reduction is a highly reversible one-electron process involving the O2/O2- couple in all of the electrolytes examined with little effect on the nature of the solvent. On the other hand, in Li+-containing electrolytes relevant to the Li-air battery, O2 reduction proceeds in a stepwise fashion to form O2-, O22- and O2- as products. These reactions in presence of Li+ are irreversible or quasi-reversible electrochemical processes and the solvents have significant influence on the kinetics, and reversibility or lack thereof, of the different reduction products. Reversible reduction of O2 to long-lived superoxide in a Li+-conducting electrolyte in DMSO has been shown for the first time here. Chapter 5 is the culmination of the thesis where the practical application of the work is demonstrated. We designed electrolytes that facilitate Li-Air rechargeability, by applying the knowledge gained from chapters 2-4. A rechargeable Li-air cell utilizing an electrolyte composed of a solution of LiPF6 in tetraethylene glycol dimethyl ether, CH3O(CH2CH 2O)4CH3 was designed, built and its performance studied. It was shown that the cell yields high capacity and can be recharged in spite the absence of catalyst in the carbon cathode. The application of X-ray diffraction to identify these products formed in a porous carbon electrode is shown here for the first time. The rechargeability of the cell was investigated by repeated charge/discharge cycling of the cell, and the factors limiting the cycle life of the cell were studied using AC impedance spectra of the cells as a function of cycle number. In conclusion, the work carried out in this research has shown that the O2 electrochemistry in organic electrolytes is substantially different from that in aqueous electrolytes. Our work has uncovered the key roles the ion conducting salts and the organic solvents play in determining the nature of the reduction products and their reversibility. The results presented here for the first time provide a rational approach to the design and selection of organic electrolyte solutions for use in the rechargeable Li-air battery. (Abstract shortened by UMI.)
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Compressed air-assisted solvent extraction (CASX) for metal removal.
Li, Chi-Wang; Chen, Yi-Ming; Hsiao, Shin-Tien
2008-03-01
A novel process, compressed air-assisted solvent extraction (CASX), was developed to generate micro-sized solvent-coated air bubbles (MSAB) for metal extraction. Through pressurization of solvent with compressed air followed by releasing air-oversaturated solvent into metal-containing wastewater, MSAB were generated instantaneously. The enormous surface area of MSAB makes extraction process extremely fast and achieves very high aqueous/solvent weight ratio (A/S ratio). CASX process completely removed Cr(VI) from acidic electroplating wastewater under A/S ratio of 115 and extraction time of less than 10s. When synthetic wastewater containing Cd(II) of 50mgl(-1) was treated, A/S ratios of higher than 714 and 1190 could be achieved using solvent with extractant/diluent weight ratio of 1:1 and 5:1, respectively. Also, MSAB have very different physical properties, such as size and density, compared to the emulsified solvent droplets, making separation and recovery of solvent from treated effluent very easy.
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plutonium from uranium and fission products in an aqueous acidic solution by use of a chelating agent. The concentration is adjusted to about 1 N bar. The aqueous solution is then contacted with a water-immiscible organic solvent solution and the chelating agent. The chelating agents covered by this invention comprise
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Reductive amination with zinc powder in aqueous media
Imperio, Daniela; Penoni, Andrea; Palmisano, Giovanni
2011-01-01
Summary Zinc powder in aqueous alkaline media was employed to perform reductive amination of aldehydes with primary amines. The corresponding secondary amines were obtained in good yields along with minor amounts of hydrodimerization byproducts. The protocol is a green alternative to the use of complex hydrides in chlorinated or highly flammable solvents. PMID:21915212
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van Boxtel, Niels; Wolfs, Kris; Van Schepdael, Ann; Adams, Erwin
2015-12-18
The sensitivity of gas chromatography (GC) combined with the full evaporation technique (FET) for the analysis of aqueous samples is limited due to the maximum tolerable sample volume in a headspace vial. Using an acetone acetal as water scavenger prior to FET-GC analysis proved to be a useful and versatile tool for the analysis of high boiling analytes in aqueous samples. 2,2-Dimethoxypropane (DMP) was used in this case resulting in methanol and acetone as reaction products with water. These solvents are relatively volatile and were easily removed by evaporation enabling sample enrichment leading to 10-fold improvement in sensitivity compared to the standard 10μL FET sample volumes for a selection of typical high boiling polar residual solvents in water. This could be improved even further if more sample is used. The method was applied for the determination of residual NMP in an aqueous solution of a cefotaxime analogue and proved to be considerably better than conventional static headspace (sHS) and the standard FET approach. The methodology was also applied to determine trace amounts of ethylene glycol (EG) in aqueous samples like contact lens fluids, where scavenging of the water would avoid laborious extraction prior to derivatization. During this experiment it was revealed that DMP reacts quantitatively with EG to form 2,2-dimethyl-1,3-dioxolane (2,2-DD) under the proposed reaction conditions. The relatively high volatility (bp 93°C) of 2,2-DD makes it possible to perform analysis of EG using the sHS methodology making additional derivatization reactions superfluous. Copyright © 2015 Elsevier B.V. All rights reserved.
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Del Mar, P.
1993-12-28
A process is presented of sample preparation prior to analysis for the concentration of an organic contaminant in an aqueous medium by (a) passing an initial aqueous medium including a minor amount of the organic contaminant through a composite tube comprised of a blend of a polyolefin and a polyester, the composite tube having an internal diameter of from about 0.1 to about 2.0 millimeters and being of sufficient length to permit the organic contaminant to adhere to the composite tube, (b) passing a solvent through the composite tube. The solvent is capable of separating the adhered organic contaminant from the composite tube. Further, an extraction apparatus is presented for sample preparation prior to analysis for the concentration of an organic contaminant in an aqueous medium. The apparatus includes a composite tube comprised of a blend of a polyolefin and a polyester. The composite tube has an internal diameter of from about 0.1 to about 2.0 millimeters and has sufficient length to permit an organic contaminant contained within an aqueous medium passed therethrough to adhere to the composite tube. 2 figures.
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NASA Astrophysics Data System (ADS)
Ali, A.; Bidhuri, P.; Uzair, S.
2014-07-01
Ultrasonic speed u, densities ρ and viscosities η of xylitol in water and in 0.001 m aqueous l-tyrosine (Tyr) and l-phenylalanine (Phe) have been measured at different temperatures. From the density and ultrasonic speed measurements apparent molar isentropic compression κ_{φ}, apparent molar isentropic compressions at infinite dilution κ_{{S,φ}}0 , experimental slope S K , hydration number n H , transfer partial molar isentropic compressibility Δ_{tr} κ_{{S,φ}}0 of xylitol from water to aqueous Tyr and Phe have been obtained. From the viscosity data, B-coefficient and B-coefficient of transfer Δ tr B of xylitol from water to aqueous Phe and Tyr at different temperatures have also been estimated. Gibbs free energies of activation of viscous flow per mole of solvent Δ μ 1 0# and per mole of solute Δ μ 2 0# have been calculated by using Feakins transition state theory for the studied systems. The calculated parameters have been interpreted in terms of solute-solute and solute-solvent interactions and hydration behavior of xylitol.
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Lu, Weidong; Alam, Md Asraful; Pan, Ying; Wu, Jingcheng; Wang, Zhongming; Yuan, Zhenhong
2016-10-01
The biomass of Chlorella sp. was pretreated with three different aqueous deep eutectic solvents (aDESs), i.e. aqueous choline chloride-oxalic acid (aCh-O), aqueous choline chloride-ethylene glycol (aCh-EG) and aqueous urea-acetamide (aU-A). The effect of aDESs pretreatment of microalgae biomass was evaluated in terms of lipid recovery rate, total carbohydrate content, fatty acid composition, and thermal chemical behavior of biomass. Results indicated that, lipid recovery rate was increased from 52.03% of untreated biomass to 80.90%, 66.92%, and 75.26% of the biomass treated by aCh-O, aCh-EG and aU-A, respectively. However, there were no major changes observed in fatty acid profiles of both untreated and treated biomass, specifically palmitic acid, palmitoleic acid and stearic acid under various pretreatments. Furthermore, characterizations of untreated and treated biomass were carried out using Fourier transform infrared (FTIR), thermogravimetry analysis (TGA) and scanning electron microscope (SEM) to understand the enhanced lipids recovery. Copyright © 2016. Published by Elsevier Ltd.
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Solvent tuning configurational conversion of lycopene aggregates in organic-aqueous mixing solvent
NASA Astrophysics Data System (ADS)
Dong, Jia; Zhang, Di; Wang, Xin-Yue; Wang, Peng
2018-06-01
In general cases, carotenoid aggregates are prepared in organic-water mixing solvent depending on its hydrophobic character. It is well-known that one of carotenoids, lycopene, is more likely to form typical H-aggregates. In this study, new type lycopene J-aggregates were prepared in DMSO-water mixing solvent with small amount of toluene, which was observed for the first time. We proposed a potential structure model combining with exciton model to interpret the mechanism of spectra changes. Our finding has provided new methods and novel ideas for controlling carotenoid aggregates formation.
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NASA Astrophysics Data System (ADS)
Anita, K.; Rajmuhon Singh, N.
2011-10-01
The complexation of thiosemicarbazide with Pr(III) and Nd(III) in absence and presence of Zn(II), a soft metal ion in aqueous and organic solvents like CH 3OH,CH 3CN, dioxane (C 4H 8O 2) and DMF (C 3H 7NO) and their equimolar mixtures are discussed by employing absorption difference and comparative absorption spectrophotometry. Complexation of thiosemicarbazide with Pr(III) and Nd(III) is indicated by the changes in the absorption intensity following the subsequent changes in the oscillator strength of different 4f-4f bands and Judd-Ofelt intensity ( Tλ) parameters. The other spectral parameters like energy interaction parameters namely Slater-Condon ( Fk), Racah ( Ek), Lande ( ξ4f), Nephelauxetic ratio ( β) and bonding parameters ( b1/2) are further computed to explain the nature of complexation. The difference in the energy parameters with respect to donor atoms and solvents reveal that the chemical environment around the lanthanide ions has great impact on f-f transition and any change in the environment result in modification of the spectra. Various solvents and their equimolar mixtures are also used to discuss the participation of solvents in the complexation.
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Akhtar, Muhammad T; Mushtaq, Mian Y; Verpoorte, Robert; Richardson, Michael K; Choi, Young H
2016-01-01
Zebrafish is a frequently employed model organism in systems medicine and biomarker discovery. A crosscutting fundamental question, and one that has been overlooked in the field, is the "system-wide" (omics) effects induced in zebrafish by metabolic solvents and culture buffers. Indeed, any bioactivity or toxicity test requires that the target compounds are dissolved in an appropriate nonpolar solvent or aqueous media. It is important to know whether the solvent or the buffer itself has an effect on the zebrafish model organism. We evaluated the effects of two organic carrier solvents used in research with zebrafish, as well as in drug screening: dimethyl sulfoxide (DMSO) and ethanol, and two commonly used aqueous buffers (egg water and Hank's balanced salt solution). The effects of three concentrations (0.01, 0.1, and 1%) of DMSO and ethanol were tested in the 5-day-old zebrafish embryo using proton nuclear magnetic resonance ((1)H NMR) based metabolomics. DMSO (1% and 0.1%, but not 0.01%) exposure significantly decreased the levels of adenosine triphosphate (ATP), betaine, alanine, histidine, lactate, acetate, and creatine (p < 0.05). By contrast, ethanol exposure did not alter the embryos' metabolome at any concentration tested. The two different aqueous media noted above impacted the zebrafish embryo metabolome as evidenced by changes in valine, alanine, lactate, acetate, betaine, glycine, glutamate, adenosine triphosphate, and histidine. These results show that DMSO has greater effects on the embryo metabolome than ethanol, and thus is used with caution as a carrier solvent in zebrafish biomarker research and oral medicine. Moreover, the DMSO concentration should not be higher than 0.01%. Careful attention is also warranted for the use of the buffers egg water and Hank's balanced salt solution in zebrafish. In conclusion, as zebrafish is widely used as a model organism in life sciences, metabolome changes induced by solvents and culture buffers warrant further attention for robust systems science, and precision biomarkers that will stand the test of time.
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Solvent extraction system for plutonium colloids and other oxide nano-particles
Soderholm, Lynda; Wilson, Richard E; Chiarizia, Renato; Skanthakumar, Suntharalingam
2014-06-03
The invention provides a method for extracting plutonium from spent nuclear fuel, the method comprising supplying plutonium in a first aqueous phase; contacting the plutonium aqueous phase with a mixture of a dielectric and a moiety having a first acidity so as to allow the plutonium to substantially extract into the mixture; and contacting the extracted plutonium with second a aqueous phase, wherein the second aqueous phase has a second acidity higher than the first acidity, so as to allow the extracted plutonium to extract into the second aqueous phase. The invented method facilitates isolation of plutonium polymer without the formation of crud or unwanted emulsions.
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Dagade, Dilip H; Shetake, Poonam K; Patil, Kesharsingh J
2007-07-05
The density and osmotic coefficient data for solutions of 15-crown-5 (15C5) in water and in CCl4 solvent systems at 298.15 K have been reported using techniques of densitometry and vapor pressure osmometry in the concentration range of 0.01-2 mol kg-1. The data are used to obtain apparent molar and partial molar volumes, activity coefficients of the components as a function of 15C5 concentration. Using the literature heat of dilution data for aqueous system, it has become possible to calculate entropy of mixing (DeltaS(mix)), excess entropy of solution (DeltaS(E)), and partial molar entropies of the components at different concentrations. The results of all these are compared to those obtained for aqueous 18-crown-6 solutions reported earlier. It has been observed that the partial molar volume of 15C5 goes through a minimum and that of water goes through a maximum at approximately 1.2 mol kg(-1) in aqueous solutions whereas the opposite is true in CCl4 medium but at approximately 0.5 mol kg(-1). The osmotic and activity coefficients of 15C5 and excess free energy change for solution exhibit distinct differences in the two solvent systems studied. These results have been explained in terms of hydrophobic hydration and interactions in aqueous solution while weak solvophobic association of 15C5 molecules in CCl4 solutions is proposed. The data are further subjected to analysis by applying McMillan-Mayer and Kirkwood-Buff theories of solutions. The analysis shows that osmotic second virial coefficient value for 15C5 is marginally less than that of 18C6 indicating that reduction in ring flexibility does not affect the energetics of the interactions much in aqueous solution while the same gets influenced much in nonpolar solvent CCl4.
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Extraction of ethanol with higher carboxylic acid solvents and their toxicity to yeast
USDA-ARS?s Scientific Manuscript database
In a screening exercise for ethanol-selective extraction solvents, partitioning of ethanol and water from a 5 wt% aqueous solution into several C8 – C18 carboxylic acids was studied. Results for the acids are compared with those from alcohols of similar structure. In all cases studied, the acids exh...
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Influence of Organic Solvents on Chalcopyrite Oxidation Ability of Thiobacillus ferrooxidans
Torma, Arpad E.; Itzkovitch, Irwin J.
1976-01-01
It has been shown that organic solvents used primarily for the extraction of metals from aqueous leach liquors decrease both the surface tension of the aqueous phase and the chalcopyrite oxidation ability of Thiobacillus ferrooxidans. For the reagents and modifiers investigated, the order of inhibition was found to be LIX 70 < LIX 73 < LIX 71 < LIX 64N < LIX 65N < TBP ∼ isodecanol ∼ nonylphenol < LIX 63 <<< D2EHPA ∼ Kelex 100 < Kelex 120 <<< Alamine 336 ∼ Alamine 308 ∼ Alamine 310 < Alamine 304 < Adogen 381 ∼ Aliquat 336 < Adogen 364. To avoid limitation in bacterial activity, organic matter should be removed from the recycling liquor prior to leaching. PMID:16345164
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NASA Astrophysics Data System (ADS)
Jajodia, S.; Chimankar, O. P.; Kalambe, A.; Goswami, S. G.
2012-12-01
Amino acids are the building blocks of the proteins; their study provides important information, about the behaviour of larger biomolecules such as proteins. The properties of proteins such as their structure, solubility, denaturation, etc. are greatly influenced by electrolytes. Ultrasonic velocity and density values have been used for evaluation of thermal expansion coefficient and adiabatic compressibility for ternary systems (amino acid/salt + water) namely L-leucine / L-asparagine each in 1.5 M aqueous solution of NaCl used as solvent for various concentrations and at different temperatures (298.15K - 323.15K). Present paper reports the variation of various thermoacoustical parameters such as Moelwyn-Hughes parameter (C1), Beyer's non-linearity parameter (B/A), internal pressure (Pi), fractional free volume (f), available volume (Va), repulsive exponent (n), molecular constant (r), van der Waals' constant (b), Debye temperatue (θD), etc. have been computed from the thermal expansion coefficient with the change of concentration and temperature. The variations of all these parameters have been interpreted in terms of various intermolecular interactions such as strong, weak, charge transfer, complex formation, hydrogen bonding interaction. The structure making and breaking properties of the interacting components existing in proposed ternary systems. It shows the associating and dissociating tendency of the molecules of solute in solvent.The hetromolecular interactions are present in both the ternary systems.
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Young, Cora J; Gómez Biagi, Rodolfo F; Hurley, Michael D; Wallington, Timothy J; Mabury, Scott A
2008-11-01
In an effort to reduce volatile organic compounds (VOCs) in paint solvents, replacements containing non-VOC compounds have been proposed. One such compound is 4-chlorobenzotrifluoride (CBTF), for which environmental fate studies have not been conducted. The objective of the present study was to determine the products of the atmospheric oxidation of CBTF and the aqueous fate of these products. Smog chamber experiments were performed to measure the kinetics and mechanism of atmospheric oxidation. A rate constant of 2.22 (+/-0.30) x 10(-13) cm3 molecule(-1) s(-1) was determined for the reaction of hydroxyl radicals with CBTF in 700 Torr of air at 296 K. Using offline sampling and gas chromatography coupled to mass spectroscopic analysis, it was determined that 2-chloro-5-trifluoromethylphenol (o-CTFP) was the primary product of CBTF atmospheric oxidation. Aqueous photolysis of o-CTFP in deionized water proceeded at a rate of 1.3 (+/-0.1) x 10(-4) s(-1), corresponding to a half-life of 1.5 +/- 0.1 h and a quantum yield of 6.6 (+/-0.4) x 10(-4). The mechanism of photolysis was investigated using liquid chromatography coupled to tandem mass spectrometry, which suggested that degradation of o-CTFP occurred via photonucleophilic displacement of chlorine, followed by photoinduced hydrolysis of the trifluoromethyl group to yield 3,4-dihydroxybenzoic acid (an approved food additive considered to be nontoxic).
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Why does high pressure destroy co-non-solvency of PNIPAm in aqueous methanol?
de Oliveira, Tiago E; Netz, Paulo A; Mukherji, Debashish; Kremer, Kurt
2015-11-28
It is well known that poly(N-isopropylacrylamide) (PNIPAm) exhibits an interesting, yet puzzling, phenomenon of co-non-solvency. Co-non-solvency occurs when two competing good solvents for PNIPAm, such as water and alcohol, are mixed together. As a result, the same PNIPAm collapses within intermediate mixing ratios. This complex conformational transition is driven by preferential binding of methanol with PNIPAm. Interestingly, co-non-solvency can be destroyed when applying high hydrostatic pressures. In this work, using a large scale molecular dynamics simulation employing high pressures, we propose a microscopic picture behind the suppression of the co-non-solvency phenomenon. Based on thermodynamic and structural analysis, our results suggest that the preferential binding of methanol with PNIPAm gets partially lost at high pressures, making the background fluid reasonably homogeneous for the polymer. This is consistent with the hypothesis that the co-non-solvency phenomenon is driven by preferential binding and is not based on depletion effects.
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Kistler, Melissa L; Liu, Tianbo; Gouzerh, Pierre; Todea, Ana Maria; Müller, Achim
2009-07-14
We report the self-assembly processes in solution of three Keplerate-type molybdenum-oxide based clusters {Mo72V30}, {Mo72Cr30} and {Mo72Fe30} (all with diameters of approximately 2.5 nm). These clusters behave as unique weak polyprotic acids owing to the external water ligands attached to the non-Mo metal centers. Whereas the Cr and Fe clusters have 30 water ligands attached at the 30 M3+ centers pointing outside, {Mo72V30} has 20 water ligands coordinated to vanadium atoms, of which only 10 are pointing outside. The self-assembly processes of the Keplerates leading to supramolecular blackberry-type structures are influenced by the effective charge densities on the cluster surfaces, which can be tuned by the pH values and solvent properties. As expected, {Mo72Cr30} and {Mo72Fe30} behave similarly in aqueous solution due to their analogous structures and in both cases the self-assembly follows the partial deprotonation of the external water ligands attached to the non-Mo metal centers. However, the M-OH2 functionalities differ not only in acidity but also lability, i.e. in different residence times of the H2O ligands. In contrast to {Mo72Cr30} and {Mo72Fe30}, the {Mo72V30} clusters carry a rather large number of negative charges so that their solution properties are different. They exist as discrete macroions in dilute aqueous solution, and form only in mixed water/organic solvent (like acetone) blackberry-type structures whose size increases with acetone content. The comparison of the properties of the clusters allows more general information about the interesting self-assembly phenomenon to be unveiled.
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Samarasinghe, Nalin; Fernando, Sandun; Faulkner, William B.
2012-12-01
The ability to extract lipids from high-moisture Nannochloris Oculata algal biomass disrupted with high pressure homogenization was investigated. During the first phase, the effect of high pressure homogenization (system pressure and number of passes) on disrupting aqueous algae (of different concentrations and degree of stress) was investigated. Secondly, the effect of degree of cell wall disruption on the amount of lipids extracted with three solvents, namely: hexane, dichloromethane and chloroform, were compared. Studies reveled that high pressure homogenization is effective on cell disruption while the amount of system pressure being the most significant factor affecting the degree of cell breakage.more » Although the number of passes had some impact, the level of disruption seemed to level-off after a certain number of passes. The study revealed that slightly polar solvents (such as chloroform and dichloromethane) performed better in aqueous-phase lipid extractions as compared to hexane. Also, it was revealed that it was not necessary to disrupt the algal cells completely to achieve appreciable levels of lipid yields. In fact, conditions that exerted only 20% of the cells to completely disrupt, allowed sufficient damage to liberate most of the lipids contained in the remainder of the cells.« less
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Mandal, Sudeb; Joardar, Soumen; Das, Saktipada; Bhattacharyya, Anjan
2011-11-09
The photodegradation of the carboxamide acaricide hexythiazox in three different solvent systems (aqueous methanolic, aqueous isopropanolic, and aqueous acetonitrilic solutions) in the presence of H(2)O(2), KNO(3), and TiO(2) under ultraviolet (UV) light (λ(max) ≥ 250 nm) and sunlight (λ(max) ≥290 nm) has been assessed in this work. The kinetics of photodecomposition of hexythiazox and the identification of photoproducts were carried out using liquid chromatography-mass spectrometry. The rate of photodecomposition of hexythiazox in different solvents followed first-order kinetics in both UV radiation and natural sunlight, and the degradation rates were faster under UV light than under sunlight. Hexythiazox was found to be more efficiently photodegraded in the presence of TiO(2) than in the presence of H(2)O(2) and KNO(3). Two major photoproducts were separated in pure form using column chromatography and identified according to IR, (1)H NMR, and mass spectral information as cyclohexylamine and 5-(4-chlorophenyl)-4-methylthiazolidin-2-one. Another nine photoproducts were identified according to LC-MS/MS spectral information. The plausible photodegradation pathways of hexythiazox were proposed according to the structures of the photoproducts.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Samarasinghe, Nalin; Fernando, Sandun; Faulkner, William B.
The ability to extract lipids from high-moisture Nannochloris Oculata algal biomass disrupted with high pressure homogenization was investigated. During the first phase, the effect of high pressure homogenization (system pressure and number of passes) on disrupting aqueous algae (of different concentrations and degree of stress) was investigated. Secondly, the effect of degree of cell wall disruption on the amount of lipids extracted with three solvents, namely: hexane, dichloromethane and chloroform, were compared. Studies reveled that high pressure homogenization is effective on cell disruption while the amount of system pressure being the most significant factor affecting the degree of cell breakage.more » Although the number of passes had some impact, the level of disruption seemed to level-off after a certain number of passes. The study revealed that slightly polar solvents (such as chloroform and dichloromethane) performed better in aqueous-phase lipid extractions as compared to hexane. Also, it was revealed that it was not necessary to disrupt the algal cells completely to achieve appreciable levels of lipid yields. In fact, conditions that exerted only 20% of the cells to completely disrupt, allowed sufficient damage to liberate most of the lipids contained in the remainder of the cells.« less
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Gavara, Raquel; Lima, João Carlos; Rodríguez, Laura
2016-05-11
The spectroscopic properties of aggregates obtained from the hydrogelator [Au(4-pyridylethynyl)(PTA)] were studied in solvents of different polarities. Inspection of the absorption and emission spectra of diluted solutions showed that the singlet ground state of the monomeric species is sensitive to polarity and is stabilized in more polar solvents whereas the triplet excited state is rather insensitive to changes in polarity. The study of relatively concentrated solutions revealed the presence of new emission and excitation bands at 77 K that was attributed to the presence of different kinds of aggregates. Particularly interesting behaviour was revealed in water where aggregation is observed to be more efficient. For this, absorption, emission quantum yields and luminescence lifetimes of aqueous solutions at different concentrations were investigated in more detail. These data permitted one to correlate the increase of non-radiative and radiative rate constants of the low lying triplet emissive state with concentration, and therefore with the low limit concentration for aggregation, due to the shortening of the AuAu average distances in the aggregates and consequent enhancement of the spin-orbit coupling in the system.
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Nondestructive reactivation of chemical protective garments. Final report, June 1985-July 1989
DOE Office of Scientific and Technical Information (OSTI.GOV)
Chang, K.W.; Chang, S.Y.; Klemperer, E.
In the near future, chemical protective combat uniforms may be worn by Army personnel on a continuous basis. Activated carbon, the operative component, has diminished capacity for sorbing chemical agents after it has been exposed to dirt, sweat, cigarette smoke, engine exhaust, petroleum products and numerous other elements routinely present in the battlefield environment. This report summarizes the development of two nondestructive methods for cleaning and reactivating soiled chemical protective garments. Complete reactivation was achieved when the aqueous i-propanol iodine displacement method of Manes, which removed all but pure hydrocarbon oil soils from the current overgarment Type III foam ormore » Kynol activated carbon fiber material, was applied in nonaqueous solvent. Subsequently, a nonaqueous solvent method that requires less handling was chosen in designing a truck-mounted system. It features non-agitative flow of methylene chloride and methanol around the chemical-protective garments suspended between ultrasonic transducers. Both methods restore full sorptivity to the Type III foam liner. There is a one-time 10% loss of activated carbon without any loss of sorptivity. The volatile solvents are more easily removed, and can be economically recovered. Overall features of a mobile unit have been sketched.« less
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SOLVENT EXTRACTION PROCESS FOR SEPARATING ACTINIDE AND LANTHANIDE METAL VALUES
Hildebrandt, R.A.; Hyman, H.H.; Vogler, S.
1962-08-14
A process of countercurrently extracting an aqueous mineral acid feed solution for the separation of actinides from lanthanides dissolved therern is described. The feed solution is made acid-defrcient with alkali metal hydroxide prior to.contact with acid extractant; during extraction, however, acid is transferred from organic to aqueous solution and the aqueous solution gradually becomes acid. The acid-deficient phase ' of the process promotes the extraction of the actinides, while the latter acid phase'' of the process improves retention of the lanthanides in the aqueous solution. This provides for an improved separation. (AEC)
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Wybraniec, Sławomir; Stalica, Paweł; Jerz, Gerold; Klose, Bettina; Gebers, Nadine; Winterhalter, Peter; Spórna, Aneta; Szaleniec, Maciej; Mizrahi, Yosef
2009-10-09
Polar betacyanin pigments together with betaxanthins from ripe cactus fruits of Hylocereus polyrhizus (Cactaceae) were fractionated by means of preparative ion-pair high-speed countercurrent chromatography (IP-HSCCC) also using the elution-extrusion (EE) approach for a complete pigment recovery. HSCCC separations were operated in the classical 'head-to-tail' mode with an aqueous mobile phase. Different CCC solvent systems were evaluated in respect of influence and effectiveness of fractionation capabilities to separate the occurring pigment profile of H. polyrhizus. For that reason, the additions of two different volatile ion-pair forming perfluorinated carboxylic acids (PFCA) were investigated. For a direct comparison, five samples of Hylocereus pigment extract were run on preparative scale (900 mg) in 1-butanol-acetonitrile-aqueous TFA 0.7% (5:1:6, v/v/v) and the modified systems tert.-butyl methyl ether-1-butanol-acetonitrile-aqueous PFCA (2:2:1:5, v/v/v/v) using 0.7% and 1.0% trifluoroacetic acid (TFA) or heptafluorobutyric acid (HFBA) in the aqueous phase, respectively. The chemical affinity to the organic stationary CCC solvent phases and in consequence the retention of these highly polar betalain pigments was significantly increased by the use of the more lipophilic fluorinated ion-pair reagent HFBA instead of TFA. The HFBA additions separated more effectively the typical cacti pigments phyllocactin and hylocerenin from betanin as well as their iso-forms. Unfortunately, similar K(D) ratios and selectivity factors alpha around 1.0-1.1 in all tested solvent systems proved that the corresponding diastereomers, 15S-type pigments cannot be resolved from the 15R-epimers (iso-forms). Surprisingly, additions of the stronger ion-pair reagent (HFBA) resulted in a partial separation of hylocerenin from phyllocactin which were not resolved in the other solvent systems. The pigments were detected by means of HPLC-DAD and HPLC-electrospray ionization-MS using also authentic reference materials.
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Ex-Situ and In-Situ Ellipsometric Studies of the Thermal Oxide on InP
1990-12-06
ion---- Distribution/ Availabilit ? Codes£v l llt Codes Avail and/or Dist| Special Abstract The thermally grown InP oxide as etched by an aqueous...aqueous NH4OH/NH4F, and Law(17) has reported observations of orientational ordering of water and organic solvents on pyrex surfaces by in-situ...minutes, followed by a sequence of acetone, deionized water (d. i. water ) rinse. After being dipped in a concentrated aqueous HF solution for 15 seconds
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Brown, K. B.; Crouse, Jr., D. J.; Moore, J. G.
1959-03-10
A liquid-liquid extraction method is presented for recovering uranium values from an aqueous acidic solution by means of certain high molecular weight amine fn the amine classes of primary, secondary, heterocyclic secondary, tertiary, or heterocyclic tertiary. The uranium bearing aqueous acidic solution is contacted with the selected anine dissolved in a nonpolar waterimmiscible organfc solvent such as kerosene. The uranium which is substantially completely extracted by the organic phase may be stripped therefrom by water, and recovered from the aqueous phase by treatment into ammonia to precipitate ammonium diuranate.
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Brown, K.B.; Crouse, D.J. Jr.; Moore, J.G.
1959-03-10
A liquid-liquid extraction method is presented for recovering uranium values from an aqueous acidic solution by means of certain high molecular weight amine in the amine classes of primary, secondary, heterocyclic secondary, tertiary, or heterocyclic tertiary. The uranium bearing aqueous acidic solution is contacted with the selected amine dissolved in a nonpolar water-immiscible organic solvent such as kerosene. The uranium which is substantially completely exiracted by the organic phase may be stripped therefrom by waters and recovered from the aqueous phase by treatment into ammonia to precipitate ammonium diuranate.
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SOLVENT EXTRACTION OF THORIUM VALUES FROM AQUEOUS SOLUTIONS
Warf, J.C.
1959-04-21
The separation of thorium values from rare earth metals contained ln aqueous solutions by means of extraction with a water immiscible alkyl phosphate diluted with a hydrocarbon such as hexane is described. While the extraction according to this invention may be carried out from any aqueous salt solution, it is preferred to use solutions containing free mineral acid. Hydrochloric acid and in particular nitric acid are sultable in a concentration ranging from 0.1 to 7 normal. The higher acid concentration results in higher extraction values.
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NASA Astrophysics Data System (ADS)
Wijaya, Emmy C.; Separovic, Frances; Drummond, Calum J.; Greaves, Tamar L.
2018-05-01
There has been a substantial increase in enzyme applications within the biochemical and pharmaceutical industries, for example, as industrial biocatalysts. However, enzymes have narrow marginal stability which makes them prone to become inactive and/or denature with a slight change in the solvent environment. Typically industrial applications require harsher solvent environments than enzyme native environments, and hence there is a need to understand solvent-protein interactions in order to develop strategies to maintain, or enhance, the enzymatic activity under industrially relevant solvent conditions. Previously we have shown that protic ionic liquids (PILs) with water can have a stabilising effect on lysozyme, with a large variation dependent on which PIL ions are present, and the water concentration [E. C. Wijaya et al., Phys. Chem. Chem. Phys. 18(37), 25926-25936 (2016)]. Here we extend on this work using non-stoichiometric aqueous PIL solvents to investigate, and isolate, the role of pH and ionicity on enzymes. We have used the PILs ethylammonium nitrate (EAN) and ethanolammonium formate (EOAF) since our previous work has identified these as good solvents for lysozyme. Solvent libraries were made from these two PILs with an additional precursor acid or base to modify the acidity/basicity of the neutral stoichiometric PIL, and with water added, to have solutions with 4-17 mol. % of the PIL ions in water. Molar ratios of base:acid were varied between 1:1.05 and 2:1 for EAN and 1:1.25 and 2:1 for EOAF, which enabled from highly basic to highly acidic solutions to be obtained. This was to modify the acidity/basicity of the neutral stoichiometric PILs, without the addition of buffers. The structure and stability of hen egg white lysozyme (HEWL) were explored under these solvent conditions using synchrotron small angle X-ray scattering (SAXS), Fourier transform infrared (FTIR), and activity assays. The radius of gyration and Kratky plots obtained from the SAXS data showed little change with varying ionicity or acid:base ratio. FTIR showed that α-helix was maintained in all, except for the most acidic solvent conditions. The activity data show that HEWL was active between pH 0 and 11 for the EA:N-water system and pH 4.4 and 11 for the EOA:F-water system. This work indicates that ionic liquids have the potential to enable enzymes to maintain activity across a broader range of solvent conditions.
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de La Harpe, Kimberly; Kohl, Forrest R; Zhang, Yuyuan; Kohler, Bern
2018-03-08
To better understand how the solvent influences excited-state deactivation in DNA strands, femtosecond time-resolved IR (fs-TRIR) pump-probe measurements were performed on a d(AT) 9 ·d(AT) 9 duplex dissolved in a deep eutectic solvent (DES) made from choline chloride and ethylene glycol in a 1:2 mol ratio. This solvent, known as ethaline, is a member of a class of ionic liquids capable of solubilizing DNA with minimal disruption to its secondary structure. UV melting analysis reveals that the duplex studied here melts at 18 °C in ethaline compared to 50 °C in aqueous solution. Ethaline has an excellent transparency window that facilitates TRIR measurements in the double-bond stretching region. Transient spectra recorded in deuterated ethaline at room temperature indicate that photoinduced intrastrand charge transfer occurs from A to T, yielding the same exciplex state previously detected in aqueous solution. This state decays via charge recombination with a lifetime of 380 ± 10 ps compared to the 300 ± 10 ps lifetime measured earlier in D 2 O solution. The TRIR data strongly suggest that the long-lived exciplex forms exclusively in the solvated duplex, and not in the denatured single strands, which appear to have little, if any, base stacking. The longer lifetime of the exciplex state in the DES compared to aqueous solution is suggested to arise from reduced stabilization of the charge transfer state, resulting in slower charge recombination on account of Marcus inverted behavior.
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Solvent exchange method: a novel microencapsulation technique using dual microdispensers.
Yeo, Yoon; Chen, Alvin U; Basaran, Osman A; Park, Kinam
2004-08-01
A new microencapsulation method called the "solvent exchange method" was developed using a dual microdispenser system. The objective of this research is to demonstrate the new method and understand how the microcapsule size is controlled by different instrumental parameters. The solvent exchange method was carried out using a dual microdispenser system consisting of two ink-jet nozzles. Reservoir-type microcapsules were generated by collision of microdrops of an aqueous and a polymer solution and subsequent formation of polymer films at the interface between the two solutions. The prepared microcapsules were characterized by microscopic methods. The ink-jet nozzles produced drops of different sizes with high accuracy according to orifice size of a nozzle, flow rate of the jetted solutions, and forcing frequency of the piezoelectric transducers. In an individual microcapsule, an aqueous core was surrounded by a thin polymer membrane; thus, the size of the collected microcapsules was equivalent to that of single drops. The solvent exchange method based on a dual microdispenser system produces reservoir-type microcapsules in a homogeneous and predictable manner. Given the unique geometry of the microcapsules and mildness of the encapsulation process, this method is expected to provide a useful alternative to existing techniques in protein microencapsulation.
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NASA Astrophysics Data System (ADS)
Du, Yong; Xue, Jiadan; Cai, Qiang; Zhang, Qi
2018-02-01
Vibrational spectroscopic methods, including terahertz absorption and Raman scattering spectroscopy, were utilized for the characterization and analysis of gamma-aminobutyric acid (GABA), benzoic acid (BA), and the corresponding GABA-BA cocrystal formation under various pH values of aqueous solution. Vibrational spectroscopic results demonstrated that the solvent GABA-BA cocrystal, similar as grinding counterpart, possessed unique characteristic features compared with that of starting parent compounds. The change of vibrational modes for GABA-BA cocrystal comparing with starting components indicates there is strong inter-molecular interaction between GABA and BA molecules during its cocrystallization process. Formation of GABA-BA cocrystal under slow solvent evaporation is impacted by the pH value of aqueous solution. Vibrational spectra indicate that the GABA-BA cocrystal could be stably formed with the solvent condition of 2.00 ≤ pH ≤ 7.00. In contrast, such cocrystallization did not occur and the cocrystal would dissociate into its parent components when the pH value of solvent is lower than 2.00. This study provides experimental benchmark to discriminate and identify the structure of cocrystal and also pH-dependent cocrystallization effect with vibrational spectroscopic techniques in solid-state pharmaceutical fields.
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Solvent Extraction Separation of Trivalent Americium from Curium and the Lanthanides
DOE Office of Scientific and Technical Information (OSTI.GOV)
Jensen, Mark P.; Chiarizia, Renato; Ulicki, Joseph S.
2015-02-27
The sterically constrained, macrocyclic, aqueous soluble ligand N,N'-bis[(6-carboxy-2-pyridyl)methyl]-1,10-diaza-18-crown-6 (H2BP18C6) was investigated for separating americium from curium and all the lanthanides by solvent extraction. Pairing H2BP18C6, which favors complexation of larger f-element cations, with acidic organophosphorus extractants that favor extraction of smaller f-element cations, such as bis-(2-ethylhexyl)phosphoric acid (HDEHP) or (2-ethylhexyl)phosphonic acid mono(2-ethylhexyl) ester (HEH[EHP]), created solvent extraction systems with good Cm/Am selectivity, excellent trans-lanthanide selectivity (Kex,Lu/Kex,La = 108), but poor selectivity for Am against the lightest lanthanides. However, using an organic phase containing both a neutral extractant, N,N,N’,N’-tetra(2-ethylhexyl)diglycolamide (TEHDGA), and HEH[EHP] enabled rejection of the lightest lanthanides during loading ofmore » the organic phase from aqueous nitric acid, eliminating their interference in the americium stripping stages. In addition, although it is a macrocyclic ligand, H2BP18C6 does not significantly impede the mass transfer kinetics of the HDEHP solvent extraction system« less
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Enhanced Mixed Feedstock Processing Using Ionic Liquids
DOE Office of Scientific and Technical Information (OSTI.GOV)
Simmons, Blake A
2016-10-22
Biomass pretreatment using certain ionic liquids (ILs) is very efficient, generally producing a substrate that is amenable to saccharification with fermentable sugar yields approaching theoretical limits. Although promising, several challenges must be addressed before IL pretreatment technology becomes commercially viable. Once of the most significant challenges is the affordable and scalable recovery and recycle or the IL itself. Pervaporation is a highly selective and scalable membrane separation process for quantitatively recovering volatile solutes or solvents directly from non-volatile solvents that could prove more versatile for IL dehydration than traditional solvent extraction processes, as well as efficient and energetically more advantageousmore » than standard evaporative techniques. In this study we evaluated a commercially available pervaporation system for IL dehydration and recycling as part of an integrated IL pretreatment process using 1-ethyl-3-methylimidazolium acetate ([C2C1Im][OAc]) that has been proven to be very effective as a biomass pretreatment solvent. We demonstrate that >99.9 wt% [C2C1Im][OAc] can be recovered from aqueous solution and recycled at least five times. A preliminary techno-economic analysis validated the promising role of pervaporation in improving overall biorefinery process economics, especially in the case where other IL recovery technologies might lead to significant losses. These findings establish the foundation for further development of pervaporation as an effective method of recovering and recycling ILs using a commercially viable process technology.« less
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Solvent extraction separation of Th-227 and Ac-225 in room temperature ionic liquids
DOE Office of Scientific and Technical Information (OSTI.GOV)
Bell, Jason R; Boll, Rose Ann; Dai, Sheng
2012-01-01
The solvent extractions of Th-227 and Ac-225 from the aqueous phase into ionic liquids (ILs) were investigated by using N,N,N ,N - tetraoctyldiglycolamide (TODGA) or di(2-ethylhexyl)phosphoric acid (HDEHP) as an extractant. Four ionic liquids, 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([C4mim][NTf2]), 1-butyl-3-methylimidazolium bis(perfluoroethanesulfonyl)imide ([C4mim][BETI]), 1-butyl-2,3-trimethyleneimidazolium (trifluoromethanesulfonyl)imide [BuI5][NTf2], and 1-benzyl pyridinium bis(trifluoromethanesulfonyl)imide ([PhCH2Py][NTf2]) were used as extraction solvents for separation of Th-227 and Ac-225 in this study. Excellent extraction efficiencies and selectivities were found for Th-227/Ac-225 when HDEHP was used as an extractant in these ionic liquids. The effects of different extractant concentrations in ionic liquids and acidities of the aqueous phase on extraction efficienciesmore » and selectivities of Th-227/Ac-225 are also presented in this article.« less
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Raffaini, Giuseppina; Milani, Roberto; Ganazzoli, Fabio; Resnati, Giuseppe; Metrangolo, Pierangelo
2016-01-01
Hydrophobins are proteins of interest for numerous applications thanks to their unique conformational and surface properties and their ability to self-assemble at interfaces. Here we report fully atomistic molecular mechanics and molecular dynamics results together with circular dichroism experimental data, aimed to study the conformational properties of the hydrophobin HFBII in a fluorinated solvent in comparison with a water solution and/or at an aqueous/vacuum interface. Both the atomistic simulations and the circular dichroism data show the remarkable structural stability of HFBII at all scales in all these environments, with no significant structural change, although a small cavity is formed in the fluorinated solvent. The combination of theoretical calculations and circular dichroism data can describe in detail the protein conformation and flexibility in different solvents and/or at an interface, and constitutes a first step towards the study of their self-assembly. Copyright © 2015 Elsevier Inc. All rights reserved.
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Elucidating the influence of polymorph-dependent interfacial solvent structuring at chitin surfaces.
Brown, Aaron H; Walsh, Tiffany R
2016-10-20
Interfacial solvent structuring is thought to be influential in mediating the adsorption of biomolecules at aqueous materials interfaces. However, despite the enormous potential for exploitation of aqueous chitin interfaces in industrial, medical and drug-delivery applications, little is known at the molecular-level about such interfacial solvent structuring for chitin. Here we use molecular simulation to predict the structure of the [100] and [010] interfaces of α-chitin and β-chitin dihydrate in contact with liquid water and saline solution. We find the α-chitin [100] interface supports lateral high-density regions in the first water layer at the interface, which are also present, but not as pronounced, for β-chitin. The lateral structuring of interfacial ions at the saline/chitin interface is also more pronounced for α-chitin compared with β-chitin. Our findings provide a foundation for the systematic design of biomolecules with selective binding affinity for different chitin polymorphs. Copyright © 2016 Elsevier Ltd. All rights reserved.
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Extractant composition including crown ether and calixarene extractants
Meikrantz, David H.; Todd, Terry A.; Riddle, Catherine L.; Law, Jack D.; Peterman, Dean R.; Mincher, Bruce J.; McGrath, Christopher A.; Baker, John D.
2009-04-28
An extractant composition comprising a mixed extractant solvent consisting of 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 DtBu18C6 may be present at from approximately 0.01M to approximately 0.4M, such as at 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 at 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 extractant composition further comprises an aqueous phase. The mixed extractant solvent may be used to remove cesium and strontium from the aqueous phase.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Amann, J.M.G.; Bouallou, C.
2009-04-15
This work focuses on the development of a new solvent for CO{sub 2} capture. This new solvent is an aqueous solution with a blend of N-methyldiethanolamine (MDEA) and triethylene tetramine (TETA), an amine with four amino groups. CO{sub 2} absorption was investigated between 298 and 333 K using a Lewis cell with a constant interfacial area. Several concentrations of MDEA (17.5 and 40 wt %) and TETA (3 and 6 wt %) were assessed. The influence of the CO{sub 2} partial pressure on the absorption rate was pointed out. The addition of small amount of TETA leads to a highmore » increase in the CO{sub 2} absorption rates. A numerical model based on the film theory was used to determine the rate coefficients between CO{sub 2} and TETA for the different solvents. The physicochemical parameters have a huge influence on the determination of the rate coefficients.« less
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Temperature-Dependent Implicit-Solvent Model of Polyethylene Glycol in Aqueous Solution.
Chudoba, Richard; Heyda, Jan; Dzubiella, Joachim
2017-12-12
A temperature (T)-dependent coarse-grained (CG) Hamiltonian of polyethylene glycol/oxide (PEG/PEO) in aqueous solution is reported to be used in implicit-solvent material models in a wide temperature (i.e., solvent quality) range. The T-dependent nonbonded CG interactions are derived from a combined "bottom-up" and "top-down" approach. The pair potentials calculated from atomistic replica-exchange molecular dynamics simulations in combination with the iterative Boltzmann inversion are postrefined by benchmarking to experimental data of the radius of gyration. For better handling and a fully continuous transferability in T-space, the pair potentials are conveniently truncated and mapped to an analytic formula with three structural parameters expressed as explicit continuous functions of T. It is then demonstrated that this model without further adjustments successfully reproduces other experimentally known key thermodynamic properties of semidilute PEG solutions such as the full equation of state (i.e., T-dependent osmotic pressure) for various chain lengths as well as their cloud point (or collapse) temperature.
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NASA Technical Reports Server (NTRS)
Palm, D. E.; Shue, S. G.; Keil, L. C.; Balaban, C. D.; Severs, W. B.
1995-01-01
The effects of atrial natriuretic peptide (ANP), vasopressin (AVP) and angiotensin (ANG) on blood and intraocular pressures of pentobarbital anesthetized rats were evaluated following intravenous, intracerebroventricular or anterior chamber routes of administration. Central injections did not affect intraocular pressure. Equipressor intravenous infusions of ANG raised, whereas AVP decreased, intraocular pressure. Direct infusions of a balanced salt solution (0.175 microliter/min) raised intraocular pressure between 30 and 60 min. Adding ANG or ANP slightly reduced this solvent effect but AVP was markedly inhibitory. An AVP-V1 receptor antagonist reversed the blunting of the solvent-induced rise by the peptide, indicating receptor specificity. Acetazolamide pretreatment lowered intraocular pressure, but the solvent-induced rise in intraocular pressure and inhibition by AVP still occurred without altering the temporal pattern. Thus, these effects appear unrelated to aqueous humor synthesis rate. The data support the possibility of intraocular pressure regulation by peptides acting from the blood and aqueous humor.
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Kinetic Studies that Evaluate the Solvolytic Mechanisms of Allyl and Vinyl Chloroformate Esters
D’Souza, Malcolm J.; Givens, Aaron F.; Lorchak, Peter A.; Greenwood, Abigail E.; Gottschall, Stacey L.; Carter, Shannon E.; Kevill, Dennis N.
2013-01-01
At 25.0 °C the specific rates of solvolysis for allyl and vinyl chloroformates have been determined in a wide mix of pure and aqueous organic mixtures. In all the solvents studied, vinyl chloroformate was found to react significantly faster than allyl chloroformate. Multiple correlation analyses of these rates are completed using the extended (two-term) Grunwald-Winstein equation with incorporation of literature values for solvent nucleophilicity (NT) and solvent ionizing power (YCl). Both substrates were found to solvolyze by similar dual bimolecular carbonyl-addition and unimolecular ionization channels, each heavily dependent upon the solvents nucleophilicity and ionizing ability. PMID:23549265
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Skavdahl, R.E.; Mason, E.A.
1962-06-01
An investigation of the solvent extraction characteristics of the nitro and nitrato complexes of nitrosylruthenium in nitric acid- sodium nitrate aqueous media was conducted. As the organic extractant phase, a solution of trilaurylamine (TLA) in toluene was utilized. In addition to the usual process parameter variation tyne of experiment, a rapid dilution type of experiment was used extensively to determine qualitative and semiquantitative results regarding the degree of extractability and concentration of the more extractable species of the nitrato complexes of nitrosylruthenium. It was found that the acids of the tetra-nitrato and pentanitrato complexes were the more extractable species formore » that set of complexes and that the acid of the penta-nitrato complex was the more extractable of the two. It was observed that for freshly prepared solutions, the dinitro complex of nitrosylruthenium was much more extractable than the gross nitrato complexes solutions. Nitro complexes in general, and the dinitro complex in particular, may be the controlling agent in ruthenium decontamination of spent nuclear fuel processed by solvent extraction methods. The experimental results from both sets of complexes could be more meaningfully correlated on the basis of unbound nitric acid concentration in the organic phase than on the basis of nitric acid concentration in the aqueous phase. The extraction of nitric acid by TLA from nitric acid-sodium nitrate aqueous solutions was investigated and the results correlated on the basis of activity of the undissociated nitric acid in the aqueous phase. (auth)« less
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High throughput screening of CO2 solubility in aqueous monoamine solutions.
Porcheron, Fabien; Gibert, Alexandre; Mougin, Pascal; Wender, Aurélie
2011-03-15
Post-combustion Carbon Capture and Storage technology (CCS) is viewed as an efficient solution to reduce CO(2) emissions of coal-fired power stations. In CCS, an aqueous amine solution is commonly used as a solvent to selectively capture CO(2) from the flue gas. However, this process generates additional costs, mostly from the reboiler heat duty required to release the carbon dioxide from the loaded solvent solution. In this work, we present thermodynamic results of CO(2) solubility in aqueous amine solutions from a 6-reactor High Throughput Screening (HTS) experimental device. This device is fully automated and designed to perform sequential injections of CO(2) within stirred-cell reactors containing the solvent solutions. The gas pressure within each reactor is monitored as a function of time, and the resulting transient pressure curves are transformed into CO(2) absorption isotherms. Solubility measurements are first performed on monoethanolamine, diethanolamine, and methyldiethanolamine aqueous solutions at T = 313.15 K. Experimental results are compared with existing data in the literature to validate the HTS device. In addition, a comprehensive thermodynamic model is used to represent CO(2) solubility variations in different classes of amine structures upon a wide range of thermodynamic conditions. This model is used to fit the experimental data and to calculate the cyclic capacity, which is a key parameter for CO(2) process design. Solubility measurements are then performed on a set of 50 monoamines and cyclic capacities are extracted using the thermodynamic model, to asses the potential of these molecules for CO(2) capture.
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Wang, Junmei; Hou, Tingjun
2011-12-01
In this work, we have evaluated how well the general assisted model building with energy refinement (AMBER) force field performs in studying the dynamic properties of liquids. Diffusion coefficients (D) have been predicted for 17 solvents, five organic compounds in aqueous solutions, four proteins in aqueous solutions, and nine organic compounds in nonaqueous solutions. An efficient sampling strategy has been proposed and tested in the calculation of the diffusion coefficients of solutes in solutions. There are two major findings of this study. First of all, the diffusion coefficients of organic solutes in aqueous solution can be well predicted: the average unsigned errors and the root mean square errors are 0.137 and 0.171 × 10(-5) cm(-2) s(-1), respectively. Second, although the absolute values of D cannot be predicted, good correlations have been achieved for eight organic solvents with experimental data (R(2) = 0.784), four proteins in aqueous solutions (R(2) = 0.996), and nine organic compounds in nonaqueous solutions (R(2) = 0.834). The temperature dependent behaviors of three solvents, namely, TIP3P water, dimethyl sulfoxide, and cyclohexane have been studied. The major molecular dynamics (MD) settings, such as the sizes of simulation boxes and with/without wrapping the coordinates of MD snapshots into the primary simulation boxes have been explored. We have concluded that our sampling strategy that averaging the mean square displacement collected in multiple short-MD simulations is efficient in predicting diffusion coefficients of solutes at infinite dilution. Copyright © 2011 Wiley Periodicals, Inc.
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Matteucci, Federica; Ercole, Claudia; del Gallo, Maddalena
2015-01-01
Perchloroethene, trichloroethene, and other chlorinated solvents are widespread groundwater pollutants. They form dense non-aqueous phase liquids that sink through permeable groundwater aquifers until non-permeable zone is reached. In Italy, there are many situations of serious contamination of groundwater that might compromise their use in industry, agriculture, private, as the critical case of a Central Italy valley located in the province of Teramo (“Val Vibrata”), characterized by a significant chlorinated solvents contamination. Data from the various monitoring campaigns that have taken place over time were collected, and new samplings were carried out, resulting in a complete database. The data matrix was processed with a multivariate statistic analysis (in particular principal component analysis, PCA) and was then imported into geographic information system (GIS), to obtain a model of the contamination. A microcosm anaerobic study was utilized to assess the potential for in situ natural or enhanced bioremediation. Most of the microcosms were positive for dechlorination, particularly those inoculated with a mineral medium. This indicate the presence of an active native dechlorinating population in the subsurface, probably inhibited by co-contaminants in the groundwater, or more likely by the absence or lack of nutritional factors. Among the tested electron donors (i.e., yeast extract, lactate, and butyrate) lactate and butyrate enhanced dechlorination of chlorinated compounds. PCA and GIS studies allowed delimiting the contamination; the microcosm study helped to identify the conditions to promote the bioremediation of the area. PMID:26388862
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Solvent Dependence of Lateral Charge Transfer in a Porphyrin Monolayer
Brennan, Bradley J.; Regan, Kevin P.; Durrell, Alec C.; ...
2016-12-19
Lateral charge transport in a redox)active monolayer can be utilized for solar energy harvesting. We chose the porphyrin system to study the influence of the solvent on lateral hole hopping, which plays a crucial role in the charge)transfer kinetics. We also examined the influence of water, acetonitrile, and propylene carbonate as solvents. Hole)hopping lifetimes varied by nearly three orders of magnitude among solvents, ranging from 3 ns in water to 2800 ns in propylene carbonate, and increased nonlinearly as a function of added acetonitrile in aqueous solvent mixtures. Our results elucidate the important roles of solvation, molecular packing dynamics, andmore » lateral charge)transfer mechanisms that have implications for all dye)sensitized photoelectrochemical device designs.« less
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Yan, Chih-Hao; Wu, Hui-Fen
2004-01-01
A liquid-phase microextraction (LPME) method has been demonstrated for the extraction and determination of organochlorine pesticides (OCPs) in aqueous solution. The method combines a dual gauge microsyringe with a hollow fiber membrane (LPME/DGM-HF) followed by detection by gas chromatography/ion trap mass spectrometry (GC/ITMS). The advantages include speed, low solvent and sample consumption, simplicity and ease of use. The extraction time, solvent selection, salt concentration and sample stirring rate have been investigated in order to optimize extraction efficiency. The viability is evaluated by measuring the linearity and detection limit of the five OCPs in aqueous solution. Detection linearity for the OCPs has been achieved over a range of concentrations between 1 and 500 microg/L (r2 > 0.930), with a detection limit of 0.1 microg/L for each OCP. Copyright 2004 John Wiley & Sons, Ltd.
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NASA Astrophysics Data System (ADS)
Dong, L.; Zheng, D. X.; Wei, Z.; Wu, X. H.
2009-10-01
By investigating the vapor pressure of the solvent and the affinity between ionic liquids (ILs) and the solvent, it is proposed that 1,3-dimethylimidazolium chloride ([Mmim]Cl) has the potential to be used as a novel absorbent species with the absorption cycle working fluid. Adopting a high-pressure reaction kettle, the method of gas-liquid phase reaction was used to synthesize [Mmim]Cl under the conditions of 348.15 K and 0.7 MPa. The densities of [Mmim]Cl aqueous solutions were measured for mass fractions in the range from 20% to 90% at 293.15 K, 298.15 K, 303.15 K, 308.15 K, 313.15 K, and 318.15 K with a digital vibrating-tube densimeter. The excess volume, the apparent molar volume, the partial molar volume, and the apparent molar expansibility of this system were investigated, and the influences of variations of the cation and anion on the density of several IL aqueous solutions are discussed.
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Hu, Michael Z.
2006-05-23
Disclosed is a method for making amorphous spherical particles of zirconium titanate and crystalline spherical particles of zirconium titanate comprising the steps of mixing an aqueous solution of zirconium salt and an aqueous solution of titanium salt into a mixed solution having equal moles of zirconium and titanium and having a total salt concentration in the range from 0.01 M to about 0.5 M. A stearic dispersant and an organic solvent is added to the mixed salt solution, subjecting the zirconium salt and the titanium salt in the mixed solution to a coprecipitation reaction forming a solution containing amorphous spherical particles of zirconium titanate wherein the volume ratio of the organic solvent to aqueous part is in the range from 1 to 5. The solution of amorphous spherical particles is incubated in an oven at a temperature .ltoreq.100.degree. C. for a period of time .ltoreq.24 hours converting the amorphous particles to fine or ultrafine crystalline spherical particles of zirconium titanate.
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Recovery of Pyruvic Acid using Tri-n-butylamine Dissolved in Non-Toxic Diluent (Rice Bran Oil)
NASA Astrophysics Data System (ADS)
Pal, Dharm; Keshav, Amit
2016-04-01
An attempt has been made to investigate the effectiveness of the vegetable oil based biocompatible solvent for the separation of pyruvic acid from fermentation broth, by using rice bran oil as natural, non-toxic diluent. Reactive extraction of pyruvic acid (0.1-0.5 k mol/m3) from aqueous solutions has been studied using tri-n-butylamine (TBA; 10-70 %) as an extractant dissolved in non toxic rice bran oil at T = 30 ± 1 °C. Results were presented in terms of distribution coefficient (Kd), extraction efficiency (E %), loading ratio (Z), and complexation constant (\\varphi_{α β }). Extraction equilibrium was interpreted using mass action modeling approach. Based on the extent of loading (Z < 0.5) only (1:1), pyruvic acid: TBA complex was proposed. Equilibrium complexation constant was evaluated to 1.22 m3/k mol. Results obtained are useful in understanding the extraction mechanism.
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NASA Astrophysics Data System (ADS)
Deosarkar, S. D.; Mendkudle, M. S.
2014-09-01
Densities (ρ), viscosities (η) and refractive indices ( n D) of aqueous sodium acetate (SA), ammonium acetate (AA), and lead acetate (LA) solutions have been measured for different concentrations of salts at 302.15 K. Apparent molar volumes (φv) for studied solutions were calculated from density data, and fitted to Masson's relation and partial molar volume (φ{v/o}) was determined. Viscosity data were fitted to Jones-Dole equation and viscosity A- and B-coefficients were determined. Refractive index and density data were fitted to Lorentz and Lorenz equation and specific refraction ( R D) were calculated. Behavior of various physicochemical properties indicated presence of strong ion-solvent interactions in present systems and the acetate salts structure maker in water.
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Method to produce water-soluble sugars from biomass using solvents containing lactones
Dumesic, James A.; Luterbacher, Jeremy S.
2015-06-02
A process to produce an aqueous solution of carbohydrates that contains C6-sugar-containing oligomers, C6 sugar monomers, C5-sugar-containing oligomers, C5 sugar monomers, or any combination thereof is presented. The process includes the steps of reacting biomass or a biomass-derived reactant with a solvent system including a lactone and water, and an acid catalyst. The reaction yields a product mixture containing water-soluble C6-sugar-containing oligomers, C6-sugar monomers, C5-sugar-containing oligomers, C5-sugar monomers, or any combination thereof. A solute is added to the product mixture to cause partitioning of the product mixture into an aqueous layer containing the carbohydrates and a substantially immiscible organic layer containing the lactone.
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Method to produce water-soluble sugars from biomass using solvents containing lactones
Dumesic, James A.; Luterbacher, Jeremy S.
2017-08-08
A process to produce an aqueous solution of carbohydrates that contains C6-sugar-containing oligomers, C6 sugar monomers, C5-sugar-containing oligomers, C5 sugar monomers, or any combination thereof is presented. The process includes the steps of reacting biomass or a biomass-derived reactant with a solvent system including a lactone and water, and an acid catalyst. The reaction yields a product mixture containing water-soluble C6-sugar-containing oligomers, C6-sugar monomers, C5-sugar-containing oligomers, C5-sugar monomers, or any combination thereof. A solute is added to the product mixture to cause partitioning of the product mixture into an aqueous layer containing the carbohydrates and a substantially immiscible organic layer containing the lactone.
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Measurement of dielectric constant of organic solvents by indigenously developed dielectric probe
NASA Astrophysics Data System (ADS)
Keshari, Ajay Kumar; Rao, J. Prabhakar; Rao, C. V. S. Brahmmananda; Ramakrishnan, R.; Ramanarayanan, R. R.
2018-04-01
The extraction, separation and purification of actinides (uranium and plutonium) from various matrices are an important step in nuclear fuel cycle. One of the separation process adopted in an industrial scale is the liquid-liquid extraction or solvent extraction. Liquid-liquid extraction uses a specific ligand/extractant in conjunction with suitable diluent. Solvent extraction or liquid-liquid extraction, involves the partitioning of the solute between two immiscible phases. In most cases, one of the phases is aqueous, and the other one is an organic solvent. The solvent used in solvent extraction should be selective for the metal of interest, it should have optimum distribution ratio, and the loaded metal from the organic phase should be easily stripped under suitable experimental conditions. Some of the important physical properties which are important for the solvent are density, viscosity, phase separation time, interfacial surface tension and the polarity of the extractant.
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Heteroatom incorporated coke for electrochemical cell electrode
Lewis, I.C.; Greinke, R.A.
1997-06-17
This invention relates to an electrode for a coke/alkali metal electrochemical cell comprising: (a) calcined coke particles: (1) that contain at least 0.5 weight percent of nitrogen heteroatoms and at least 1.0 weight percent sulfur heteroatoms, and (2) that have an average particle size from 2 microns to 40 microns with essentially no particles being greater than 50 microns and (b) a binder. This invention also relates to a coke/alkali metal electrochemical cell comprising: (a) an electrode as described above, (b) a non-aqueous electrolytic solution comprising an organic aprotic solvent and an electrically conductive salt, and (c) a counterelectrode. 5 figs.
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Re-Usable Thin-Layer Spectroelectrochemical Cell for Non-Aqueous Solvent Systems.
1987-11-01
rapidly reassembied. It can be used under 1-gassei .I I. wIII aquleous solution or a variety of comon rg-an Ic 1 ,+.t r . -, 1 1 soivenrts , u( h as o...for 1 days. Lithium chloride (Anachemia, reagent grade) was dried at 12ooC for 24 h. Water was purified by double distillation over KMnO4, foiluwed by...peak to peaK 3eparatiun witn ;r-’ra.in scan rate from Ib mV at lmV/s to lUU mV at lUU mv/. r-eaK IC , ,:.ik ;eparatiurts measured at several scan rates
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Letseka, Thabiso
2017-01-01
We report the application of the dispersive liquid-liquid microextraction coupled to hollow-fibre membrane-assisted liquid-phase microextraction and its application for extraction of atrazine and triclosan. Under optimum conditions, namely, 25 μL of a 1 : 4 chlorobenzene : ethyl acetate mixture dispersed in 1 mL of aqueous sample, 10% (m/v) NaCl, a magnetic stirrer speed at 600 rpm, and 10 minutes' extraction time with toluene-filled fibre as the acceptor phase, the method demonstrates sufficient figures of merit. These include linearity (R2 ≥ 0.9975), intravial precision (%RSD ≤ 7.6), enrichment factors (127 and 142), limits of detection (0.0081 and 0.0169 µg/mL), and recovery from river water and sewerage (96–101%). The relatively high detection limits are attributed to the flame ionization detector which is less preferred than a mass spectrometer in trace analyses. This is the first report of a homogenous mixture of the dispersed organic solvent in aqueous solutions and its employment in extraction of organic compounds from aqueous solutions. It therefore adds yet another candidate in the pool of miniaturised solvent microextraction techniques. PMID:29158736
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Measuring CO 2 and N 2 O Mass Transfer into GAP-1 CO 2 –Capture Solvents at Varied Water Loadings
DOE Office of Scientific and Technical Information (OSTI.GOV)
Whyatt, Greg A.; Zwoster, Andy; Zheng, Feng
This paper investigates the CO 2 and N 2 O absorption behavior in the water-lean gamma amino propyl (GAP)-1/TEG solvent system using a wetted-wall contactor. Testing was performed on a blend of GAP-1 aminosilicone in triethylene glycol at varied water loadings in the solvent. Measurements were made with CO 2 and N 2 O at representative lean (0.04 mol CO 2/mol alkalinity), middle (0.13 mol CO 2 /mol alkalinity) and rich (0.46 mol CO 2 /mol alkalinity) solvent loadings at 0, 5, 10 and 15 wt% water loadings at 40, 60 and 80C° and N 2 O at (0.08-0.09 molmore » CO 2 /mol alkalinity) at 5 wt% water at 40, 60 and 80C°. CO 2 flux was found to be non-linear with respect to log mean pressure driving force (LMPD). Liquid-film mass transfer coefficients (k'g) were calculated by subtracting the gas film resistance (determined from a correlation from literature) from the overall mass transfer measurement. The resulting k'g values for CO 2 and N 2 O in GAP-1/TEG mixtures were found to be higher than that of 5M aqueous monoethanolamine under comparable driving force albeit at higher solvent viscosities. The k'g values for CO 2 were also found to decrease with increasing solvent water content and increase with a decrease in temperature. These observations indicate that mass transfer of CO 2 in GAP-1/TEG is linked to the physical solubility of CO 2 , which is higher in organic solvents compared to water. This paper expands on the understanding of the unique mass transfer behavior and kinetics of CO 2 capture in water-lean solvents.« less
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Cantu, David C.; Lee, Juntaek; Lee, Mal -Soon; ...
2016-03-28
The deployment of transformational non-aqueous CO 2-capture solvent systems is encumbered by high viscosity even at intermediate uptakes. Using single-molecule CO 2 binding organic liquids as a prototypical example, we identify the key molecular features controlling bulk liquid viscosity and CO 2 uptake kinetics. Fast uptake kinetics arise from close proximity of the alcohol and amine sites that are involved in CO 2 binding. This process results in the concerted formation of a Zwitterion containing both an alkylcarbonate and a protonated amine. The hydrogen bonding between the two functional groups ultimately determines the solution viscosity. Based on molecular simulation, thismore » work reveals options to significantly reduce viscosity with molecular modifications that shift the proton transfer equilibrium towards a neutral acid/amine species as opposed to the ubiquitously accepted Zwitterionic state. Lastly, the molecular design concepts proposed here, for the alkyl-carbonate systems, are readily extensible to other CO 2 capture technologies, such as the carbamate- or imidazole-based solvent chemistries.« less
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On a relationship between molecular polarizability and partial molar volume in water.
Ratkova, Ekaterina L; Fedorov, Maxim V
2011-12-28
We reveal a universal relationship between molecular polarizability (a single-molecule property) and partial molar volume in water that is an ensemble property characterizing solute-solvent systems. Since both of these quantities are of the key importance to describe solvation behavior of dissolved molecular species in aqueous solutions, the obtained relationship should have a high impact in chemistry, pharmaceutical, and life sciences as well as in environments. We demonstrated that the obtained relationship between the partial molar volume in water and the molecular polarizability has in general a non-homogeneous character. We performed a detailed analysis of this relationship on a set of ~200 organic molecules from various chemical classes and revealed its fine well-organized structure. We found that this structure strongly depends on the chemical nature of the solutes and can be rationalized in terms of specific solute-solvent interactions. Efficiency and universality of the proposed approach was demonstrated on an external test set containing several dozens of polyfunctional and druglike molecules.
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Selvaraju, K; Kirubavathi, K
2013-11-01
The single crystals of bis l-proline hydrogen nitrate (BLPHN) belonging to non-centrosymmetric space group were successfully grown by the slow evaporation solution growth technique. The BLPHN crystals of size 10×7×3mm(3) were obtained in 35days. Initially, the solubility tests were carried out for two solvents such as deionized water and mixed of deionized water-acetone. Among the two solvents, the solubility of BLPHN was found to be the highest in deionized water, so crystallization of BLPHN was done from its aqueous solution. As grown, crystals were characterized by single crystal X-ray diffraction studies and optical transmission spectral studies. Infrared spectroscopy, thermo gravimetric analysis and differential thermal analysis measurements were performed to study the molecular vibration and thermal behavior of the grown BLPHN crystals. Nonlinear optical (NLO) behavior of BLPHN crystal was studied by Kurtz and Perry powder method. Copyright © 2013 Elsevier B.V. All rights reserved.
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Ochiai, Nobuo; Sasamoto, Kikuo; David, Frank; Sandra, Pat
2016-07-15
A novel solvent-assisted stir bar sorptive extraction (SA-SBSE) technique was developed for enhanced recovery of polar solutes in aqueous samples. A conventional PDMS stir bar was swollen in several solvents with log Kow ranging from 1.0 to 3.5 while stirring for 30min prior to extraction. After extraction, thermal desorption - gas chromatography - (tandem) mass spectrometry (TD-GC-(MS/)MS) or liquid desorption - large volume injection (LD-LVI)-GC-MS were performed. An initial study involved investigation of potential solvents for SA-SBSE by weighing of the residual solvent in the swollen PDMS stir bar before and after extraction. Compared to conventional SBSE, SA-SBSE using diethyl ether, methyl isobutyl ketone, dichloromethane, diisopropyl ether and toluene provided higher recoveries from water samples for test solutes with log Kow<2.5. For SA-SBSE using dichloromethane, recoveries were improved by factors of 1.4-4.1, while maintaining or even improving the recoveries for test solutes with log Kow>2.5. The performance of the SA-SBSE method using dichloromethane, diisopropyl ether, and cyclohexane is illustrated with analyses of aroma compounds in beer and of pesticides in wine. Copyright © 2016 The Authors. Published by Elsevier B.V. All rights reserved.
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Thermodynamics of DL-alanine solvation in water-dimethylsulfoxide mixtures at 298.15 K
NASA Astrophysics Data System (ADS)
Roy, S.; Mahali, K.; Mondal, S.; Dolui, B. K.
2015-04-01
In this study we mainly discuss the transfer Gibbs free energy Δ G {/t 0}( i) and Δ S {/t 0}( i)entropy of DL-alanine at 298.15 K and consequently the involved chemical transfer free energy (Δ G {/t,ch 0}( i)) and entropy ( TΔ S {/t,ch 0}( i)) in aqueous mixtures of dimethylsulfoxide are discussed to clarify the solvation chemistry of DL-alanine. For the evaluation of these energy terms, solubility of this amino acid has been measured by formol titrimetry at five equidistant temperatures i.e., from 288.15 to 308.15 K in different composition of this mixed solvent system. The various solvent parameters as well as thermodynamic parameters like molar volume, density, dipole moment and solvent diameter of this solvent system have also been reported here. The chemical effects of the transfer Gibbs energies (Δ G {/t,ch 0}( i)) and entropies of transfer ( TΔ S {/t,ch 0}( i)) have been obtained after elimination of cavity effect and dipole-dipole interaction effects from the total transfer energies. Here the chemical contribution of transfer energetics of DL-alanine is mainly guided by the composite effects of increased dispersion interaction, basicity effect and decreased acidity, hydrogen bonding effects, hydrophilic hydration and hydrophobic hydration of aqueous DMSO mixtures as compared to that of reference solvent, water.
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Farajzadeh, Mir Ali; Sattari Dabbagh, Masoumeh; Yadeghari, Adeleh
2017-05-01
In this study, a gas-assisted dispersive liquid-phase microextraction method using a deep eutectic solvent as the extraction solvent combined with gas chromatography and flame ionization detection was developed for the extraction and determination of some pesticide residues in vegetable and fruit juice samples. In this method, choline chloride and 4-chlorophenol at a molar ratio of 1:2 were mixed. By heating and vortexing, a clear, water-immiscible, and homogeneous liquid was formed. The obtained deep eutectic solvent was added to an aqueous solution of the analytes in a conical test tube. Air was bubbled into the aqueous solution and a cloudy solution was obtained. During this step, the analytes were extracted into the fine droplets of the extraction solvent. After centrifugation, an aliquot of the settled phase was injected into the separation system. Under the optimum extraction conditions, enrichment factors, and extraction recoveries were obtained in the ranges of 247-355 and 49-71%, respectively. The obtained values for the limits of detection and quantification were in the ranges of 0.24-1.4 and 0.71-4.2 μg/L, respectively. The proposed method is simple, fast, efficient, and inexpensive. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Tahan, A; Monajjemi, M
2011-12-01
Quantum mechanical and molecular dynamics methods were used to analyze the structure and stability of neutral and zwitterionic configurations of the extracted active site sequence from a Burkholderia cepacia lipase, histidyl-seryl-glutamin (His86-Ser87-Gln88) and its mutated form, histidyl-cysteyl-glutamin (His86-Cys87-Gln88) in vacuum and different solvents. The effects of solvent dielectric constant, explicit and implicit water molecules and side chain mutation on the structure and stability of this sequence in both neutral and zwitterionic forms are represented. The quantum mechanics computations represent that the relative stability of zwitterionic and neutral configurations depends on the solvent structure and its dielectric constant. Therefore, in vacuum and the considered non-polar solvents, the neutral form of the interested sequences is more stable than the zwitterionic form, while their zwitterionic form is more stable than the neutral form in the aqueous solution and the investigated polar solvents in most cases. However, on the potential energy surfaces calculated, there is a barrier to proton transfer from the positively charged ammonium group to the negatively charged carboxylat group or from the ammonium group to the adjacent carbonyl oxygen and or from side chain oxygen and sulfur to negatively charged carboxylat group. Molecular dynamics simulations (MD) were also performed by using periodic boundary conditions for the zwitterionic configuration of the hydrated molecules in a box of water molecules. The obtained results demonstrated that the presence of explicit water molecules provides the more compact structures of the studied molecules. These simulations also indicated that side chain mutation and replacement of sulfur with oxygen leads to reduction of molecular flexibility and packing.
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Method of separating lignocellulosic material into lignin, cellulose and dissolved sugars
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.
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Method of separating lignocellulosic material into lignin, cellulose and dissolved sugars
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.
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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.
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DOE Office of Scientific and Technical Information (OSTI.GOV)
Tingey, J.M.; Fulton, J.L.; Smith, R.D.
1990-03-08
The van der Waals attractive interactions between aqueous droplets in water-in-oil type microemulsions have been investigated for a range of continuous-phase solvents including the alkanes from methane to isooctane and the noble gases, krypton and xenon. Hamaker constants for water droplets with surfactant shells of the sodium bis(2-ethylhexyl) sulfosuccinate (AOT) in subcritical and supercritical solvents were calculated by using Lifshitz theory and the resulting interaction potential calculations qualitatively account for many features of the phase behavior of these systems.
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Fragrance compounds and amphiphilic association structures.
Friberg, S E
1998-05-01
Fragrance formulations have traditionally been based on alcohol as the solvent, but the recent legal restrictions on volatile organic solvents have prompted the industry to change to aqueous solubilized systems. The article reviews the fundamental factors in the application of such systems evaluating the influence by different amphiphilic association structures on the vapor pressure of fragrance compounds. This information is subsequently used to estimate the variation of fragrance compound vapor pressures during evaporation. The results reveal that the vapor pressure versus time variation is improved compared to solvent-based formulations.
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NASA Astrophysics Data System (ADS)
Wendlandt, R. F.; Foremski, J. J.
2013-12-01
Laboratory experiments show that it is possible to integrate (1) the chemistry of serpentine dissolution, (2) capture of CO2 gas from the combustion of natural gas and coal-fired power plants using aqueous amine-based solvents, (3) long-term CO2 sequestration via solid phase carbonate precipitation, and (4) capture solvent regeneration with acid recycling in a single, continuous process. In our process, magnesium is released from serpentine at 300°C via heat treatment with ammonium sulfate salts or at temperatures as low as 50°C via reaction with sulfuric acid. We have also demonstrated that various solid carbonate phases can be precipitated directly from aqueous amine-based (NH3, MEA, DMEA) CO2 capture solvent solutions at room temperature. Direct precipitation from the capture solvent enables regenerating CO2 capture solvent without the need for heat and without the need to compress the CO2 off gas. We propose that known low-temperature electrochemical methods can be integrated with this process to regenerate the aqueous amine capture solvent and recycle acid for dissolution of magnesium-bearing mineral feedstocks and magnesium release. Although the direct precipitation of magnesite at ambient conditions remains elusive, experimental results demonstrate that at temperatures ranging from 20°C to 60°C, either nesquehonite Mg(HCO3)(OH)●2H2O or a double salt with the formula [NH4]2Mg(CO3)2●4H2O or an amorphous magnesium carbonate precipitate directly from the capture solvent. These phases are less desirable for CO2 sequestration than magnesite because they potentially remove constituents (water, ammonia) from the reaction system, reducing the overall efficiency of the sequestration process. Accordingly, the integrated process can be accomplished with minimal energy consumption and loss of CO2 capture and acid solvents, and a net generation of 1 to 4 moles of H2O/6 moles of CO2 sequestered (depending on the solid carbonate precipitate and amount of produced H2 and O2 gas reacted to produce heat and water). Features of the integrated process include the following: 1) the four separate processes have compatible chemistry, enabling design of an integrated, continuous process scheme for CO2 capture and sequestration; 2) all 4 stages of the process can be conducted at ambient or slightly elevated temperatures; 3) precipitating carbonate directly from the capture solvent eliminates the need for costly CO2 gas compression; and 4) recycling the acid used for serpentine dissolution and the solvent used for CO2 capture reduces feed stock costs.
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Hidaka, Hisao; Tsukamoto, Tohru; Mitsutsuka, Yoshihiro; Oyama, Toshiyuki; Serpone, Nick
2015-05-01
Agrochemicals such as the insecticide Fipronil that bear fluoro groups are generally fat-soluble and nearly insoluble in water, so that their photodegradation in a heterogeneous aqueous gallium oxide dispersion presents some challenges. This article examined the photodegradation of this insecticide by solubilizing it through the addition of organic solvents (EtOH, MeOH, THF, 1,4-dioxane and ethylene glycol) to an aqueous medium and then subjecting the insecticide to 254 nm UVC radiation under photocatalytically inert (Ga2O3/N2) and air-equilibrated (Ga2O3/O2) conditions, as well as photochemically in the absence of Ga2O3 but also under inert and air-equilibrated conditions. Defluorination, dechlorination, desulfonation and denitridation of Fipronil were examined in mixed aqueous/organic media (10, 25 and 50 vol% in organic solvent). After 3 h of UVC irradiation (50 vol% mixed media) defluorination with Ga2O3/N2 was ∼65% greater than in aqueous media, and ca. 80% greater than the direct photolysis of Fipronil under inert (N2) conditions; under air-equilibrated conditions both Ga2O3-photocatalyzed and photochemical defluorination were significantly lower than in aqueous media. Dechlorination of Fipronil was ∼160% (Ga2O3/N2) and 140% (photochemically, N2) greater than in aqueous media; under air-equilibrated conditions, both photocatalyzed and photochemical formation of Cl(-) ions in mixed media fell rather short relative to aqueous media. The photocatalyzed (Ga2O3/N2) and photochemical (N2) conversion of the sulfur group in Fipronil to SO4(2(-)) ions was ca. 20% and 30% greater, respectively, in mixed media, while under air-equilibrated conditions photocatalyzed desulfonation was nearly twofold less than in the aqueous phase; direct photolysis showed little variations in mixed media. Denitridation of the nitrogens in Fipronil occurred mostly through the formation of ammonia (as NH4(+)) under all conditions with negligible quantities of NO3(-); again mixed media offered enhanced denitridation, particularly under inert N2 conditions. Time-of-flight electrospray (TOF-MS/ESI(-)) mass spectrometry revealed a fairly large number of intermediates formed in the degradation of Fipronil, particularly under photocatalytic conditions. Only a couple of intermediates were identified in the photodegradation and the presence of Ga2O3 enhanced the complexity of an already cumbersome problem owing to the involvement of organic solvents.
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ALKYL PYROPHOSPHATE METAL SOLVENT EXTRACTANTS AND PROCESS
Long, R.L.
1958-09-30
A process is presented for the recovery of uranium from aqueous mineral acidic solutions by solvent extraction. The extractant is a synmmetrical dialkyl pyrophosphate in which the alkyl substituents have a chain length of from 4 to 17 carbon atoms. Mentioned as a preferred extractant is dioctyl pyrophosphate. The uranium is precipitated irom the organic extractant phase with an agent such as HF, fluoride salts. alcohol, or ammonia.
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Abbasghorbani, Maryam; Attaran, Abdolmohammad; Payehghadr, Mahmood
2013-01-01
In this research, solvent-assisted dispersive micro-SPE was introduced as a simple modified technique for the determination of parabens in water and cosmetic samples. Aminopropyl-functionalized magnetite nanoparticles (MNPs) were successfully synthesized and applied. GC with photoionization detector was used for the separation and detection of parabens. In this method, hexylacetate (15 μL) as a solvent and aminopropyl-functionalized MNPs (5 μg) as a sorbent were added to an aqueous sample (10 mL) and then the sample was sonicated. Dispersed magnetite was collected in the bottom of the conical tube by using a strong magnet and then ACN was added as a desorption solvent. Forty microliters of this solvent was transferred into a microvial and then acetic anhydride and pyridine were added, thus derivatization was performed by acetic anhydride. After evaporation, 1 μL of derivatized sample was injected into a gas chromatograph for analysis. Several important parameters, such as kind of organic solvent, desorption solvent and volume, amount of aminopropyl-functionalized MNPs and effect of salt addition were investigated. Under optimum conditions, the limits of detection achieved were between 50 and 300 ng/L, with RSDs (n = 5) lower than 8%. Under the optimum conditions, the enrichment factors ranged from 217 to 1253 and the extraction recoveries ranged from 10 to 62%. The recoveries were obtained for the analytes in river water and mouthwash solution and hand cream in the range of 87-103%. The advantages of proposed method are simplicity of operation, rapidity, high extraction yields, and environmental friendly character. © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
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Solvent kinetic isotope effects of human placental alkaline phosphatase in reverse micelles.
Huang, T M; Hung, H C; Chang, T C; Chang, G G
1998-01-01
Human placental alkaline phosphatase was embedded in a reverse micellar system prepared by dissolving the surfactant sodium bis(2-ethylhexyl) sulphosuccinate (Aerosol-OT) in 2,2, 4-trimethylpentane. This microemulsion system provides a convenient instrumental tool to study the possible kinetic properties of the membranous enzyme in an immobilized form. The pL (pH/p2H) dependence of hydrolysis of 4-nitrophenyl phosphate has been examined over a pL range of 8.5-12.5 in both aqueous and reverse micellar systems. Profiles of log V versus pL were Ha-bell shaped in the acidic region but reached a plateau in the basic region in which two pKa values of 9.01-9.71 and 9.86-10.48, respectively, were observed in reverse micelles. However, only one pKa value of 9.78-10.27 in aqueous solution was detected. Profiles of log V/K versus pL were bell-shaped in the acidic region. However, they were wave-shaped in the basic region in which a residue of pKa 9.10-9.44 in aqueous solution and 8.07-8.78 in reverse micelles must be dehydronated for the reaction to reach an optimum. The V/K value shifted to a lower value upon dehydronation of a pKa value of 9.80-10.62 in aqueous solution and 11.23-12.17 in reverse micelles. Solvent kinetic isotope effects were measured at three pL values. At pL 9.5, the observed isotope effect was a product of equilibrium isotope effect and a kinetic isotope effect; at pL 10.4, the log V/K value was identical in water and deuterium. The deuterium kinetic isotope effect on V/K was 1.14 in an aqueous solution and 1.16 in reverse micelles. At pL 11.0 at which the log V values reached a plateau in either solvent system, the deuterium kinetic isotope effect on V was 2.08 in an aqueous solution and 0.62 in reverse micelles. Results from a proton inventory experiment suggested that a hydron transfer step is involved in the transition state of the catalytic reaction. The isotopic fractionation factor (pi) for deuterium for the transition state (piT) increased when the pH of the solution was raised. At pL 11.0, the piT was 1.07 in reverse micelles, which corresponds to the inverse-isotope effect of the reaction in this solvent system. Normal viscosity effects on kcat and kcat/Km were observed in aqueous solution, corresponding to a diffusional controlled physical step as the rate-limiting step. We propose that the rate-limiting step of the hydrolytic reaction changes from phosphate releasing in aqueous solution to a covalent phosphorylation or dephosphorylation step in reverse micelles. PMID:9461520
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Solvent kinetic isotope effects of human placental alkaline phosphatase in reverse micelles.
Huang, T M; Hung, H C; Chang, T C; Chang, G G
1998-02-15
Human placental alkaline phosphatase was embedded in a reverse micellar system prepared by dissolving the surfactant sodium bis(2-ethylhexyl) sulphosuccinate (Aerosol-OT) in 2,2, 4-trimethylpentane. This microemulsion system provides a convenient instrumental tool to study the possible kinetic properties of the membranous enzyme in an immobilized form. The pL (pH/p2H) dependence of hydrolysis of 4-nitrophenyl phosphate has been examined over a pL range of 8.5-12.5 in both aqueous and reverse micellar systems. Profiles of log V versus pL were Ha-bell shaped in the acidic region but reached a plateau in the basic region in which two pKa values of 9.01-9.71 and 9.86-10.48, respectively, were observed in reverse micelles. However, only one pKa value of 9.78-10.27 in aqueous solution was detected. Profiles of log V/K versus pL were bell-shaped in the acidic region. However, they were wave-shaped in the basic region in which a residue of pKa 9.10-9.44 in aqueous solution and 8.07-8.78 in reverse micelles must be dehydronated for the reaction to reach an optimum. The V/K value shifted to a lower value upon dehydronation of a pKa value of 9.80-10.62 in aqueous solution and 11.23-12.17 in reverse micelles. Solvent kinetic isotope effects were measured at three pL values. At pL 9.5, the observed isotope effect was a product of equilibrium isotope effect and a kinetic isotope effect; at pL 10.4, the log V/K value was identical in water and deuterium. The deuterium kinetic isotope effect on V/K was 1.14 in an aqueous solution and 1.16 in reverse micelles. At pL 11.0 at which the log V values reached a plateau in either solvent system, the deuterium kinetic isotope effect on V was 2.08 in an aqueous solution and 0.62 in reverse micelles. Results from a proton inventory experiment suggested that a hydron transfer step is involved in the transition state of the catalytic reaction. The isotopic fractionation factor (pi) for deuterium for the transition state (piT) increased when the pH of the solution was raised. At pL 11.0, the piT was 1.07 in reverse micelles, which corresponds to the inverse-isotope effect of the reaction in this solvent system. Normal viscosity effects on kcat and kcat/Km were observed in aqueous solution, corresponding to a diffusional controlled physical step as the rate-limiting step. We propose that the rate-limiting step of the hydrolytic reaction changes from phosphate releasing in aqueous solution to a covalent phosphorylation or dephosphorylation step in reverse micelles.
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Separation of nitrogen heterocyclic compounds from model coal tar fraction by solvent extraction
DOE Office of Scientific and Technical Information (OSTI.GOV)
Kim, S.J.; Chun, Y.J.
2005-07-01
The separation of four kinds of nitrogen heterocyclic compounds (NHCs) from a model mixture comprising NHCs (indole (In), quinoline (Q), iso-quinoline (iQ), quinaldine (Qu)), three kinds of bicyclic aromatic compounds (BACs; 1-methyl-naphthalene (IMN), 2-methyl naphthalene (2MN), dimethylnaphthalene (DMN)), biphenyl (Bp) and phenyl ether (Pe) was examined by a solvent extraction. The model mixture used as a raw material of this work was prepared according to the components and compositions contained in coal tar fraction (the temperature ranges of fraction: 240-265{sup o}C). An aqueous solution of methanol, ethanol, iso-propyl alcohol, N,N-dimethyl acetamide, DMF, formamide, N-methylformamide/methanol, and formamide/methanol were used as solvents.more » An aqueous solution of formamide was found suitable for separating NHCs contained in coal tar fraction based on distribution coefficient and selectivity. The effect of operation factors on separating NHCs was investigated by the distribution equilibrium using an aqueous solution of formamide. Increasing the operation temperature and the volume ratio of solvent to feed at initial (S/F)(o) resulted in improving the distribution coefficients of each NHC, but increasing the volume fraction of water in the solvent at initial (y(w,O)) resulted in deteriorating the distribution coefficients of each NHC. With increasing y(w,O) and (S/F)(o), the selectivities of each NHC in reference to DMN increased. Increase in operation temperature resulted in decrease in selectivities of each NHC in reference to DMN. At an experimental condition fixed, the sequence of the distribution coefficient and selectivity in reference to DMN for each NHC was In {gt} iQ {gt} Q {gt} Qu, and also the sequence of the distribution coefficient for each BAC was IMN {gt} 2MN {gt} DMN. The sequence of the distribution coefficient for entire compounds analyzed by this work was In {gt} iQ {gt} Q {gt} Qu {gt} BP {gt} 1MN {gt} 2MN {gt} Pe {gt} DMN.« less
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NASA Astrophysics Data System (ADS)
Sharma, Ravi; Thakur, R. C.
2017-07-01
In the present study, the thermodynamic properties such as partial molar volumes, partial molar expansibilities, partial molar compressibilities, partial molar heat capacities and isobaric thermal expansion coefficient of different solutions of nicotinic acid in binary aqueous mixtures of D-lactose have been determined at different temperatures (298.15, 303.15, 308.15, 313.15) K. Masson's equation is used to interpret the data in terms of solute-solute and solute-solvent interactions. In the present study it has been found that nicotinic acid behaves as structure maker in aqueous and binary aqueous mixtures of D-lactose.
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Stability of urea in solution and pharmaceutical preparations.
Panyachariwat, Nattakan; Steckel, Hartwig
2014-01-01
The stability of urea in solution and pharmaceutical preparations was analyzed as a function of temperature (25°-60°C), pH (3.11-9.67), and initial urea concentration (2.5%-20%). This study was undertaken to (i) obtain more extensive, quantitative information relative to the degradation of urea in both aqueous and non-aqueous solutions and in pharmaceutical preparations, and (ii) test the effects of initial urea concentration, pH, buffer, and temperature values on urea degradation. The stability analysis shows that urea is more stable at the pH range of 4-8 and the stability of urea decreases by increase in temperature for all pH values. Within the experimental range of temperature and initial urea concentration values, the lowest urea degradation was found with lactate buffer pH 6.0. The urea decomposition rate in solution and pharmaceutical preparations shows the dependence of the initial urea concentrations. At higher initial urea concentrations, the rate of degradation is a decreasing function with time. This suggests that the reverse reaction is a factor in the degradation of concentrated urea solution. For non-aqueous solvents, isopropanol showed the best effort in retarding the decomposition of urea. Since the losses in urea is directly influenced by its stability at a given temperature and pH, the stability analysis of urea by the proposed model can be used to prevent the loss and optimize the operating condition for urea-containing pharmaceutical preparations.
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Mechanisms of catalytic cleavage of benzyl phenyl ether in aqueous and apolar phases
DOE Office of Scientific and Technical Information (OSTI.GOV)
He, Jiayue; Lu, Lu; Zhao, Chen
2014-03-01
Catalytic pathways for the cleavage of ether bonds in benzyl phenyl ether (BPE) in liquid phase using Ni- and zeolite-based catalysts are explored. In the absence of catalysts, the C-O bond is selectively cleaved in water by hydrolysis, forming phenol and benzyl alcohol as intermediates, followed by alkylation. The hydronium ions catalyzing the reactions are provided by the dissociation of water at 523 K. Upon addition of HZSM-5, rates of hydrolysis and alkylation are markedly increased in relation to proton concentrations. In the presence of Ni/SiO 2, the selective hydrogenolysis dominates for cleaving the C aliphatic-O bond. Catalyzed by themore » dual-functional Ni/HZSM-5, hydrogenolysis occurs as the major route rather than hydrolysis (minor route). In apolar undecane, the non-catalytic thermal pyrolysis route dominates. Hydrogenolysis of BPE appears to be the major reaction pathway in undecane in the presence of Ni/SiO 2 or Ni/HZSM-5, almost completely suppressing radical reactions. Density functional theory (DFT) calculations strongly support the proposed C-O bond cleavage mechanisms on BPE in aqueous and apolar phases. These calculations show that BPE is initially protonated and subsequently hydrolyzed in the aqueous phase. Finally, DFT calculations suggest that the radical reactions in non-polar solvents lead to primary benzyl and phenoxy radicals in undecane, which leads to heavier condensation products as long as metals are absent for providing dissociated hydrogen.« less
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NASA Astrophysics Data System (ADS)
Bagheri Gh., A.; Yosefi rad, A.; Rezvani, M.; Roshanzamir, S.
2012-04-01
The complexation reaction of cephalosporins namely cefotaxime (CTX), cefuroxime (CRX), and cefazolin (CEFAZ) with palladium (II) ions have been studied in water and DMF in 25 °C by the spectrophotometric methods. The method is based on the formation of yellow to yellowish brown complex between palladium (II) chloride and the investigated cephalosporins in the presence of sodium lauryl sulfate (SLS) as surfactant. The complexation process was optimized in terms of pH, temperature and contact time. The stoichiometry of all the complexes was found to be 2:1 (metal ion/ligand) for CTX, CRX, and 1:2 for CEFAZ. The stoichiometry of palladium (II)-cephalosporins was estimated by mole ratio and continuous variation methods and emphasized by the KINFIT program. These drugs could be determined by measuring the absorbance of each complex at its specific λmax. The results obtained are in good agreement with those obtained using the official methods. The proposed method was successfully applied for the determination of these compounds in their dosage forms.
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Cobb, Zoe; Sellergren, Börje; Andersson, Lars I
2007-12-01
Two novel molecularly imprinted polymers (MIPs) selected from a combinatorial library of bupivacaine imprinted polymers were used for selective on-line solid-phase extraction of bupivacaine and ropivacaine from human plasma. The MIPs were prepared using methacrylic acid as the functional monomer, ethylene glycol dimethacrylate as the cross-linking monomer and in addition hydroxyethylmethacrylate to render the polymer surface hydrophilic. The novel MIPs showed high selectivity for the analytes and required fewer and lower concentrations of additives to suppress non-specific adsorption compared with a conventional MIP. This enabled the development of an on-line system for direct extraction of buffered plasma. Selective extraction was achieved without the use of time-consuming solvent switch steps, and transfer of the analytes from the MIP column to the analytical column was carried out under aqueous conditions fully compatible with reversed-phase LC gradient separation of analyte and internal standard. The MIPs showed excellent aqueous compatibility and yielded extractions with acceptable recovery and high selectivity.
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Speeding up the self-assembly of a DNA nanodevice using a variety of polar solvents
NASA Astrophysics Data System (ADS)
Kang, Di; Duan, Ruixue; Tan, Yerpeng; Hong, Fan; Wang, Boya; Chen, Zhifei; Xu, Shaofang; Lou, Xiaoding; Wei, Wei; Yurke, Bernard; Xia, Fan
2014-11-01
The specific recognition and programmable assembly properties make DNA a potential material for nanodevices. However, the more intelligent the nanodevice is, the more complicated the structure of the nanodevice is, which limits the speed of DNA assembly. Herein, to address this problem, we investigate the performance of DNA Strand Displacement Reaction (DSDR) in a mixture of polar organic solvents and aqueous buffer and demonstrate that the organic polar solvent can speed up DNA self-assembly efficiently. Taking DSDR in 20% ethanol as an example, first we have demonstrated that the DSDR is highly accelerated in the beginning of the reaction and it can complete 60% of replacement reactions (160% enhancement compared with aqueous buffer) in the first 300 seconds. Secondly, we calculated that the ΔΔG of the DSDR in 20% ethanol (-18.2 kcal mol-1) is lower than that in pure aqueous buffer (-32.6 kcal mol-1), while the activation energy is lowered by introducing ethanol. Finally, we proved that the DSDR on the electrode surface can also be accelerated using this simple strategy. More importantly, to test the efficacy of this approach in nanodevices with a complicated and slow DNA self-assembly process, we apply this strategy in the hybridization chain reaction (HCR) and prove the acceleration is fairly obvious in 20% ethanol, which demonstrates the feasibility of the proposed strategy in DNA nanotechnology and DNA-based biosensors.The specific recognition and programmable assembly properties make DNA a potential material for nanodevices. However, the more intelligent the nanodevice is, the more complicated the structure of the nanodevice is, which limits the speed of DNA assembly. Herein, to address this problem, we investigate the performance of DNA Strand Displacement Reaction (DSDR) in a mixture of polar organic solvents and aqueous buffer and demonstrate that the organic polar solvent can speed up DNA self-assembly efficiently. Taking DSDR in 20% ethanol as an example, first we have demonstrated that the DSDR is highly accelerated in the beginning of the reaction and it can complete 60% of replacement reactions (160% enhancement compared with aqueous buffer) in the first 300 seconds. Secondly, we calculated that the ΔΔG of the DSDR in 20% ethanol (-18.2 kcal mol-1) is lower than that in pure aqueous buffer (-32.6 kcal mol-1), while the activation energy is lowered by introducing ethanol. Finally, we proved that the DSDR on the electrode surface can also be accelerated using this simple strategy. More importantly, to test the efficacy of this approach in nanodevices with a complicated and slow DNA self-assembly process, we apply this strategy in the hybridization chain reaction (HCR) and prove the acceleration is fairly obvious in 20% ethanol, which demonstrates the feasibility of the proposed strategy in DNA nanotechnology and DNA-based biosensors. Electronic supplementary information (ESI) available: Experimental procedures and analytical data are provided. See DOI: 10.1039/c4nr02257b
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Hematin crystallization from aqueous and organic solvents
NASA Astrophysics Data System (ADS)
Ketchum, Megan A.; Olafson, Katy N.; Petrova, Elena V.; Rimer, Jeffrey D.; Vekilov, Peter G.
2013-09-01
Hematin crystallization is the main mechanism of detoxification of heme that is released in malaria-infected erythrocytes as a byproduct of the hemoglobin catabolism by the parasite. A controversy exists over whether hematin crystals grow from the aqueous medium of the parasite's digestive vacuole or in the lipid bodies present in the vacuole. To this end, we compare the basic thermodynamic and structural features of hematin crystallization in an aqueous buffer at pH 4.8, as in the digestive vacuole, and in water-saturated octanol that mimics the environment of the lipid nanospheres. We show that in aqueous solutions, hematin aggregation into mesoscopic disordered clusters is insignificant. We determine the solubility of the β-hematin crystals in the pH range 4.8-7.6. We image by atomic force microscopy crystals grown at pH 4.8 and show that their macroscopic and mesoscopic morphology features are incompatible with those reported for biological hemozoin. In contrast, crystals grown in the presence of octanol are very similar to those extracted from parasites. We determine the hematin solubility in water-saturated octanol at three temperatures. These solubilities are four orders of magnitude higher than that at pH 4.8, providing for faster crystallization from organic than from aqueous solvents. These observations further suggest that the lipid bodies play a role in mediating biological hemozoin crystal growth to ensure faster heme detoxification.
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Hydrogen donor solvent coal liquefaction process
Plumlee, Karl W.
1978-01-01
An indigenous hydrocarbon product stream boiling within a range of from about C.sub.1 -700.degree. F., preferably C.sub.1 -400.degree. F., is treated to produce an upgraded hydrocarbon fuel component and a component which can be recycled, with a suitable donor solvent, to a coal liquefaction zone to catalyze the reaction. In accordance therewith, a liquid hydrocarbon fraction with a high end boiling point range up to about 700.degree. F., preferably up to about 400.degree. F., is separated from a coal liquefaction zone effluent, the separated fraction is contacted with an alkaline medium to provide a hydrocarbon phase and an aqueous extract phase, the aqueous phase is neutralized, and contacted with a peroxygen compound to convert indigenous components of the aqueous phase of said hydrocarbon fraction into catalytic components, such that the aqueous stream is suitable for recycle to the coal liquefaction zone. Naturally occurring phenols and alkyl substituted phenols, found in the aqueous phase, are converted, by the addition of hydroxyl constituents to phenols, to dihydroxy benzenes which, as disclosed in copending Application Ser. Nos. 686,813 now U.S. Pat. No. 4,049,536; 686,814 now U.S. Pat. No. 4,049,537; 686,827 now U.S. Pat. No. 4,051,012 and 686,828, K. W. Plumlee et al, filed May 17, 1976, are suitable hydrogen transfer catalysts.
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Perera, Angelo S.; Thomas, Javix; Poopari, Mohammad R.; Xu, Yunjie
2016-01-01
Vibrational optical activity spectroscopies, namely vibrational circular dichroism (VCD) and Raman optical activity (ROA), have been emerged in the past decade as powerful spectroscopic tools for stereochemical information of a wide range of chiral compounds in solution directly. More recently, their applications in unveiling solvent effects, especially those associated with water solvent, have been explored. In this review article, we first select a few examples to demonstrate the unique sensitivity of VCD spectral signatures to both bulk solvent effects and explicit hydrogen-bonding interactions in solution. Second, we discuss the induced solvent chirality, or chiral transfer, VCD spectral features observed in the water bending band region in detail. From these chirality transfer spectral data, the related conformer specific gas phase spectroscopic studies of small chiral hydration clusters, and the associated matrix isolation VCD experiments of hydrogen-bonded complexes in cold rare gas matrices, a general picture of solvation in aqueous solution emerges. In such an aqueous solution, some small chiral hydration clusters, rather than the chiral solutes themselves, are the dominant species and are the ones that contribute mainly to the experimentally observed VCD features. We then review a series of VCD studies of amino acids and their derivatives in aqueous solution under different pHs to emphasize the importance of the inclusion of the bulk solvent effects. These experimental data and the associated theoretical analyses are the foundation for the proposed “clusters-in-a-liquid” approach to account for solvent effects effectively. We present several approaches to identify and build such representative chiral hydration clusters. Recent studies which applied molecular dynamics simulations and the subsequent snapshot averaging approach to generate the ROA, VCD, electronic CD, and optical rotatory dispersion spectra are also reviewed. Challenges associated with the molecular dynamics snapshot approach are discussed and the successes of the seemingly random “ad hoc explicit solvation” reported before are also explained. To further test and improve the “clusters-in-a-liquid” model in practice, future work in terms of conformer specific gas phase spectroscopy of sequential solvation of a chiral solute, matrix isolation VCD measurements of small chiral hydration clusters, and more sophisticated models for the bulk solvent effects would be highly valuable. PMID:26942177
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Sun, Hui; Zhou, Shenggao; Moore, David K; Cheng, Li-Tien; Li, Bo
2016-05-01
We design and implement numerical methods for the incompressible Stokes solvent flow and solute-solvent interface motion for nonpolar molecules in aqueous solvent. The balance of viscous force, surface tension, and van der Waals type dispersive force leads to a traction boundary condition on the solute-solvent interface. To allow the change of solute volume, we design special numerical boundary conditions on the boundary of a computational domain through a consistency condition. We use a finite difference ghost fluid scheme to discretize the Stokes equation with such boundary conditions. The method is tested to have a second-order accuracy. We combine this ghost fluid method with the level-set method to simulate the motion of the solute-solvent interface that is governed by the solvent fluid velocity. Numerical examples show that our method can predict accurately the blow up time for a test example of curvature flow and reproduce the polymodal (e.g., dry and wet) states of hydration of some simple model molecular systems.
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Sun, Hui; Zhou, Shenggao; Moore, David K.; Cheng, Li-Tien; Li, Bo
2015-01-01
We design and implement numerical methods for the incompressible Stokes solvent flow and solute-solvent interface motion for nonpolar molecules in aqueous solvent. The balance of viscous force, surface tension, and van der Waals type dispersive force leads to a traction boundary condition on the solute-solvent interface. To allow the change of solute volume, we design special numerical boundary conditions on the boundary of a computational domain through a consistency condition. We use a finite difference ghost fluid scheme to discretize the Stokes equation with such boundary conditions. The method is tested to have a second-order accuracy. We combine this ghost fluid method with the level-set method to simulate the motion of the solute-solvent interface that is governed by the solvent fluid velocity. Numerical examples show that our method can predict accurately the blow up time for a test example of curvature flow and reproduce the polymodal (e.g., dry and wet) states of hydration of some simple model molecular systems. PMID:27365866
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Sah, H
1999-01-01
The objective of this study was to investigate the behavior of three proteins at an organic solvent/water interface. To simulate the first microencapsulation step of a water-in-oil-in-water emulsion technique, a water-in-oil emulsion was prepared by emulsifying an aqueous protein solution in either methylene chloride or ethyl acetate. Phase separation was then followed to collect protein samples from the aqueous phase and the organic solvent/water interface. Their properties were assessed by sodium dodecyl sulfate-polyacrylamide gel electrophoresis and size exclusion-HPLC. Bovine serum albumin was relatively unharmed during emulsification, compared to other proteins such as ovalbumin and lysozyme. In particular, the methylene chloride treatment on ovalbumin led to the formation of a large quantity of water-insoluble, solid-like aggregates and changes in the composition of monomeric and dimeric ovalbumin species. With regard to the question of ovalbumin recovery, only 9.74 approximately 37.72% of the used ovalbumin was present in the aqueous phases after emulsification. Similar penchant was noted with lysozyme. Water-insoluble aggregates brought with by emulsification were found to be covalently bound. Interestingly, less emulsification-induced denaturing effects were observed with ethyl acetate. Our study clearly demonstrated the emulsification-induced adverse events that were detrimental to the integrity of proteins and the importance of preserving protein stability toward microencapsulation.
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Theoretical investigation on the dimerization of the deprotonated aquo ion of Al(III) in water.
Qian, Zhaosheng; Feng, Hui; Zhang, Zhenjiang; Yang, Wenjing; Jin, Jing; Miao, Qiang; He, Lina; Bi, Shuping
2009-01-21
Reaction pathways, solvent effects and energy barriers have been investigated for the dimerization of the deprotonated aquo ion of Al(III) in aqueous solution by performing supramolecule density functional theory calculations. Two competing reaction pathways were investigated, sharing a common first step and third step, i.e. the formation of the aggregate II of two aluminium monomers and the doubly bridged dimer. One pathway involves a nucleophilic attack to undercoordinated metal center in the first step and then the loss of a coordinated water molecule. Another pathway involves a water exchange reaction in the first step and then the formation of the hydroxo bridge. The calculated results indicate that both pathways I and II are possible in aqueous solution. The direct participation of the solvent water molecule facilitates the dimerization, but the extremely large solvent shifts of the energy barriers for each reaction are attributed mainly to the bulk effect. The computed activation energies for the water exchange reactions are in good agreement with the available experimental values, namely, the calculated value 37.5 kJ mol(-1) compared to the experimental value 36.4 (+/-5) kJ mol(-1). In agreement with experimental observations in aqueous solution, the calculated results favor the transformation of singly-bridged to doubly-bridged aluminium ion, which is helpful to understand the complicated hydrolytic polymerizaiton of Al(III).