Nanostructure-thermal conductivity relationships in protic ionic liquids.

PubMed

Murphy, Thomas; Varela, Luis M; Webber, Grant B; Warr, Gregory G; Atkin, Rob

2014-10-16

The thermal conductivities of nine protic ionic liquids (ILs) have been investigated between 293 and 340 K. Within this range, the thermal conductivities are between 0.18 and 0.30 W · m(-1) · K(-1). These values are higher than those typically associated with oils and aprotic ILs, but lower than those of strongly hydrogen bonding solvents like water. Weak linear decreases in thermal conductivity with temperature are noted, with the exception of ethanolammonium nitrate (EtAN) where the thermal conductivity increases with temperature. The dependence of thermal conductivity on IL type is analyzed with use of the Bahe-Varela pseudolattice theory. This theory treats the bulk IL as an array of ordered domains with intervening domains of uncorrelated structure which enable and provide barriers to heat propagation (respectively) via allowed vibrational modes. For the protic ILs investigated, thermal conductivity depends strongly on the IL cation alkyl chain length. This is because the cation alkyl chain controls the dimensions of the IL bulk nanostructure, which consists of charged (ordered domains) and uncharged regions (disordered domains). As the cation alkyl chain controls the dimensions of the disordered domains, it thus limits the thermal conductivity. To test the generality of this interpretation, the thermal conductivities of propylammonium nitrate (PAN) and PAN-octanol mixtures were examined; water selectively swells the PAN charged domain, while octanol swells the uncharged regions. Up to a certain concentration, adding water increases thermal conduction and octanol decreases it, as expected. However, at high solute concentrations the IL nanostructure is broken. When additional solvent is added above this concentration the rate of change in thermal conductivity is greatly reduced. This is because, in the absence of nanostructure, the added solvent only serves to dilute the salt solution.

New solvent-stabilized few-layer black phosphorus for antibacterial applications.

PubMed

Sun, Zhenyu; Zhang, Yuqin; Yu, Hao; Yan, Chao; Liu, Yongchao; Hong, Song; Tao, Hengcong; Robertson, Alex W; Wang, Zhuo; Pádua, Agílio A H

2018-06-22

Discovering highly efficient, environmentally friendly, and low-cost exfoliating media that can both disperse and protect black phosphorus (BP) remains a challenge. Herein, we demonstrate such a new molecule, N,N'-dimethylpropyleneurea (DMPU), for effective exfoliation and dispersion of two-dimensional BP nanosheets. A very high exfoliation efficiency of up to 16% was achieved in DMPU, significantly surpassing other good solvents. Exfoliated flakes are free from structural disorder or oxidation. Nanosheets retain high stability in DMPU even after addition of 25 vol% of common solvents. The solvation shell appears to protect the nanosheets from reacting with water and air, more remarkably than the best solvent N-cyclohexyl-2-pyrrolidone reported so far. Molecular dynamics simulations of the exfoliation process show that DMPU is among the effective solvents, although energetically it does not appear as favorable as some other amides. We also demonstrate that our exfoliated BP nanosheets exhibit excellent antimicrobial activities against both Escherichia coli and Staphylococcus aureus, outperforming other common two-dimensional materials of graphene and MoS2, suggesting promise in biomedical applications.

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

PubMed

Benson, Sven P; Pleiss, Jürgen

2014-11-11

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

Solvent wash solution

DOEpatents

Neace, J.C.

1984-03-13

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

Solvent wash solution

DOEpatents

Neace, James C.

1986-01-01

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

Degradation of palm oil empty fruit bunch (EFB) into bio-oil in sub-and supercritical solvents

NASA Astrophysics Data System (ADS)

Sarwono, Rakhman; Pusfitasari, Eka Dian

2017-01-01

Hydrothemal Liquefaction (HTL) of empty fruit bunch (EFB) of palm oil in different solvents (water, ethanol and hexane) were comparatively investigated. Experiments were carried out in an autoclave in different EFB loading of 9%, 11%, and 13%. The temperature operation was 350 oC, without any catalysts and reaction time of 5 hours. The efficiency of above solvents in terms of conversion rate, soluble liquid and carbon products were found in this experiments. The water solvent gave higher conversion rate of 35 - 36.5 %, while hexane gave conversion of 17 - 25.25 %, and ethanol gave the lower conversion rate of 12.65 - 30.3%, respectively. Increasing the EFB load decreased the conversion rate for ethanol and hexane solvents, for water there are no significant change in the conversion rate. The bio-oil as soluble liquid produced were in order of water, ethanol, and hexane solvents, respectively. The chemical properties of bio-oil products were significantly affected by the type of liquefaction solvent. The compositional of bio-oil consists of mostly of a mixture of organic acids, ketones, and esters. The hexane and ethanol solvents resulted mostly organic acids. In water solvent resulted 2-pentanone, 4-hydroxy-4-methyl and others substances. According to the bio-oil results, organic solvents resulted higher HHV compared to water solvent. The higher heating value (HHV) of the carbon products were also comparatively, ethanol solvent resulted soluble liquid with higher HHV compared to the water solvent.

NMR relaxation studies on the hydrate layer of intrinsically unstructured proteins.

PubMed

Bokor, Mónika; Csizmók, Veronika; Kovács, Dénes; Bánki, Péter; Friedrich, Peter; Tompa, Peter; Tompa, Kálmán

2005-03-01

Intrinsically unstructured/disordered proteins (IUPs) exist in a disordered and largely solvent-exposed, still functional, structural state under physiological conditions. As their function is often directly linked with structural disorder, understanding their structure-function relationship in detail is a great challenge to structural biology. In particular, their hydration and residual structure, both closely linked with their mechanism of action, require close attention. Here we demonstrate that the hydration of IUPs can be adequately approached by a technique so far unexplored with respect to IUPs, solid-state NMR relaxation measurements. This technique provides quantitative information on various features of hydrate water bound to these proteins. By freezing nonhydrate (bulk) water out, we have been able to measure free induction decays pertaining to protons of bound water from which the amount of hydrate water, its activation energy, and correlation times could be calculated. Thus, for three IUPs, the first inhibitory domain of calpastatin, microtubule-associated protein 2c, and plant dehydrin early responsive to dehydration 10, we demonstrate that they bind a significantly larger amount of water than globular proteins, whereas their suboptimal hydration and relaxation parameters are correlated with their differing modes of function. The theoretical treatment and experimental approach presented in this article may have general utility in characterizing proteins that belong to this novel structural class.

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

Riback, Joshua A.; Bowman, Micayla A.; Zmyslowski, Adam M.

A substantial fraction of the proteome is intrinsically disordered, and even well-folded proteins adopt non-native geometries during synthesis, folding, transport, and turnover. Characterization of intrinsically disordered proteins (IDPs) is challenging, in part because of a lack of accurate physical models and the difficulty of interpreting experimental results. We have developed a general method to extract the dimensions and solvent quality (self-interactions) of IDPs from a single small-angle x-ray scattering measurement. We applied this procedure to a variety of IDPs and found that even IDPs with low net charge and high hydrophobicity remain highly expanded in water, contrary to the generalmore » expectation that protein-like sequences collapse in water. Our results suggest that the unfolded state of most foldable sequences is expanded; we conjecture that this property was selected by evolution to minimize misfolding and aggregation.« less

Kirkwood-Buff Approach Rescues Overcollapse of a Disordered Protein in Canonical Protein Force Fields.

PubMed

Mercadante, Davide; Milles, Sigrid; Fuertes, Gustavo; Svergun, Dmitri I; Lemke, Edward A; Gräter, Frauke

2015-06-25

Understanding the function of intrinsically disordered proteins is intimately related to our capacity to correctly sample their conformational dynamics. So far, a gap between experimentally and computationally derived ensembles exists, as simulations show overcompacted conformers. Increasing evidence suggests that the solvent plays a crucial role in shaping the ensembles of intrinsically disordered proteins and has led to several attempts to modify water parameters and thereby favor protein-water over protein-protein interactions. This study tackles the problem from a different perspective, which is the use of the Kirkwood-Buff theory of solutions to reproduce the correct conformational ensemble of intrinsically disordered proteins (IDPs). A protein force field recently developed on such a basis was found to be highly effective in reproducing ensembles for a fragment from the FG-rich nucleoporin 153, with dimensions matching experimental values obtained from small-angle X-ray scattering and single molecule FRET experiments. Kirkwood-Buff theory presents a complementary and fundamentally different approach to the recently developed four-site TIP4P-D water model, both of which can rescue the overcollapse observed in IDPs with canonical protein force fields. As such, our study provides a new route for tackling the deficiencies of current protein force fields in describing protein solvation.

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

PubMed

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

2016-09-21

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

Membraneless organelles can melt nucleic acid duplexes and act as biomolecular filters

NASA Astrophysics Data System (ADS)

Nott, Timothy J.; Craggs, Timothy D.; Baldwin, Andrew J.

2016-06-01

Membraneless organelles are cellular compartments made from drops of liquid protein inside a cell. These compartments assemble via the phase separation of disordered regions of proteins in response to changes in the cellular environment and the cell cycle. Here we demonstrate that the solvent environment within the interior of these cellular bodies behaves more like an organic solvent than like water. One of the most-stable biological structures known, the DNA double helix, can be melted once inside the liquid droplet, and simultaneously structures formed from regulatory single-stranded nucleic acids are stabilized. Moreover, proteins are shown to have a wide range of absorption or exclusion from these bodies, and can act as importers for otherwise-excluded nucleic acids, which suggests the existence of a protein-mediated trafficking system. A common strategy in organic chemistry is to utilize different solvents to influence the behaviour of molecules and reactions. These results reveal that cells have also evolved this capability by exploiting the interiors of membraneless organelles.

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

PubMed

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

2016-10-01

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

40 CFR 148.10 - Waste specific prohibitions-solvent wastes.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 22 2010-07-01 2010-07-01 false Waste specific prohibitions-solvent wastes. 148.10 Section 148.10 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) WATER... injection unless the solvent waste is a solvent-water mixture or solvent-containing sludge containing less...

Chromatographic analysis of Polygalae Radix by online hyphenating pressurized liquid extraction

NASA Astrophysics Data System (ADS)

Song, Yuelin; Song, Qingqing; Li, Jun; Shi, Shepo; Guo, Liping; Zhao, Yunfang; Jiang, Yong; Tu, Pengfei

2016-06-01

Practicing “green analytical chemistry” is of great importance when profiling the chemical composition of complex matrices. Herein, a novel hybrid analytical platform was developed for direct chemical analysis of complex matrices by online hyphenating pressurized warm water extraction followed by turbulent flow chromatography coupled with high performance liquid chromatography-tandem mass spectrometry (PWWE-TFC-LC-MS/MS). Two parallel hollow guard columns acted as extraction vessels connected to a long narrow polyether ether ketone tube, while warm water served as extraction solvent and was delivered at a flow rate of 2.5 mL/min to generate considerable back pressure at either vessel. A column oven heated both the solvent and crude materials. A TFC column, which is advantageous for the comprehensive trapping of small molecular substances from fluids under turbulent flow conditions, was employed to transfer analytes from the PWWE module to LC-MS/MS. Two electronic valves alternated each vessel between extraction and elution phases. As a proof-of-concept, a famous herbal medicine for the treatment of neurodegenerative disorders, namely Polygalae Radix, was selected for the qualitative and quantitative analyses. The results suggest that the hybrid platform is advantageous in terms of decreasing time, material, and solvent consumption and in its automation, versatility, and environmental friendliness.

Molecular Dynamics Analysis of Lysozyme Protein in Ethanol- Water Mixed Solvent

DTIC Science & Technology

2012-01-01

molecular dynamics simulations of solvent effect on lysozyme protein, using water, ethanol, and different concentrations of water-ethanol mixtures as...understood. This work focuses on detailed molecular dynamics simulations of solvent effect on lysozyme protein, using water, ethanol, and different...using GROMACS molecular dynamics simulation (MD) code. Compared to water environment, the lysozyme structure showed remarkable changes in water

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.

Probing the Hofmeister series beyond water: Specific-ion effects in non-aqueous solvents.

PubMed

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.

Effect of reduced use of organic solvents on disability pension in painters

PubMed Central

Järvholm, Bengt; Burdorf, Alex

2017-01-01

Objective To investigate whether the decreased use of paints based on organic solvents has caused a decreased risk for neuropsychiatric disorders in painters by studying their incidence in disability pensions. Methods The incidence of disability pension in Swedish painters who had participated in health examinations between 1971 and 1993 was studied through linkage with Swedish registers of disability pension over 1971–2010 and compared with the incidence in other construction workers as woodworkers, concrete workers and platers. When phasing out began in the 1970s, about 40% of paints were based on organic solvents and it had decreased to 4% in 1990s. The analysis was adjusted for age, time period, body mass index and smoking. Results The painters (n=23 065) had an increased risk of disability pension due to neurological diagnosis (n=285, relative risk (RR) 1.92, 95% CI 1.67 to 2.20) and psychiatric diagnosis (n=632, RR=1.61, 95 % CI 1.42 to 1.82). For neurological disorders there was a time trend with a continuously decreasing risk from 1980 onwards, but there was no such trend for psychiatric disorders. Conclusions High exposure to organic solvents increased the risk for disability pension in neurological disorders, and the risk decreased when the use of organic solvents decreased. The painters also had an increased risk of disability pension due to psychiatric disorders, but the causes have to be further investigated. PMID:28780566

The fate of proteins in outer space.

PubMed

Seddon, Gavin M; Bywater, Robert P

2017-01-01

It is well established that any properly conducted biophysical studies of proteins must take appropriate account of solvent. For water-soluble proteins it has been an article of faith that water is largely responsible for stabilizing the fold, a notion that has recently come under increasing scrutiny. Further, there are some instances when proteins are studied experimentally in the absence of solvent, as in matrix-assisted laser desorption/ionization or electrospray mass spectrometry, for example, or in organic solvents for protein engineering purposes. Apart from these considerations, there is considerable speculation as to whether there is life on planets other than Earth, where conditions including the presence of water (both in liquid or vapor form and indeed ice), temperature and pressure may be vastly different from those prevailing on Earth. Mars, for example, has only 0.6% of Earth's mean atmospheric pressure which presents profound problems to protein structures, as this paper and a large corpus of experimental work demonstrate. Similar objections will most likely apply in the case of most exoplanets and other bodies such as comets whose chemistry and climate are still largely unknown. This poses the question, how do proteins survive in these different environments? In order to cast some light on these issues we have conducted a series of molecular dynamics simulations on protein dehydration under a variety of conditions. We find that, while proteins undergoing dehydration can retain their integrity for a short duration they ultimately become disordered, and we further show that the disordering can be retarded if superficial water is kept in place on the surface. These findings are compared with other published results on protein solvation in an astrobiological and astrochemical setting. Inter alia, our results suggest that there are limits as to what to expect in terms of the existence of possible extraterrestrial forms as well to what can be achieved in experimental investigations on living systems despatched from Earth. This finding may appear to undermine currently held hopes that life will be found on nearby planets, but it is important to be aware that the presence of ice and water are by themselves not sufficient; there has to be an atmosphere which includes water vapor at a sufficiently high partial pressure for proteins to be active. A possible scenario in which there has been a history of adequate water vapor pressure which allowed organisms to prepare for a future dessicated state by forming suitable protective capsules cannot of course be ruled out.

The fate of proteins in outer space

NASA Astrophysics Data System (ADS)

Seddon, Gavin M.; Bywater, Robert Paul

2017-01-01

It is well established that any properly conducted biophysical studies of proteins must take appropriate account of solvent. For water-soluble proteins it has been an article of faith that water is largely responsible for stabilizing the fold, a notion that has recently come under increasing scrutiny. Further, there are some instances when proteins are studied experimentally in the absence of solvent, as in matrix-assisted laser desorption/ionization or electrospray mass spectrometry, for example, or in organic solvents for protein engineering purposes. Apart from these considerations, there is considerable speculation as to whether there is life on planets other than Earth, where conditions including the presence of water (both in liquid or vapour form and indeed ice), temperature and pressure may be vastly different from those prevailing on Earth. Mars, for example, has only 0.6% of Earth's mean atmospheric pressure which presents profound problems to protein structures, as this paper and a large corpus of experimental work demonstrate. Similar objections will most likely apply in the case of most exoplanets and other bodies such as comets whose chemistry and climate are still largely unknown. This poses the question, how do proteins survive in these different environments? In order to cast some light on these issues we have conducted a series of molecular dynamics simulations on protein dehydration under a variety of conditions. We find that, while proteins undergoing dehydration can retain their integrity for a short duration they ultimately become disordered, and we further show that the disordering can be retarded if superficial water is kept in place on the surface. These findings are compared with other published results on protein solvation in an astrobiological and astrochemical setting. Inter alia, our results suggest that there are limits as to what to expect in terms of the existence of possible extraterrestrial forms as well to what can be achieved in experimental investigations on living systems despatched from Earth. This finding may appear to undermine currently held hopes that life will be found on nearby planets, but it is important to be aware that the presence of ice and water are by themselves not sufficient; there has to be an atmosphere which includes water vapour at a sufficiently high partial pressure for proteins to be active. A possible scenario in which there has been a history of adequate water vapour pressure which allowed organisms to prepare for a future desiccated state by forming suitable protective capsules cannot of course be ruled out.

Evaluation of solvent effect on the extraction of phenolic compounds and antioxidant capacities from the berries: application of principal component analysis.

PubMed

Boeing, Joana Schuelter; Barizão, Erica Oliveira; E Silva, Beatriz Costa; Montanher, Paula Fernandes; de Cinque Almeida, Vitor; Visentainer, Jesuí Vergilio

2014-01-01

This study evaluated the effect of the solvent on the extraction of antioxidant compounds from black mulberry (Morus nigra), blackberry (Rubus ulmifolius) and strawberry (Fragaria x ananassa). Different extracts of each berry were evaluated from the determination of total phenolic content, anthocyanin content and antioxidant capacity, and data were applied to the principal component analysis (PCA) to gain an overview of the effect of the solvent in extraction method. For all the berries analyzed, acetone/water (70/30, v/v) solvent mixture was more efficient solvent in the extracting of phenolic compounds, and methanol/water/acetic acid (70/29.5/0.5, v/v/v) showed the best values for anthocyanin content. Mixtures of ethanol/water (50/50, v/v), acetone water/acetic acid (70/29.5/0.5, v/v/v) and acetone/water (50/50, v/v) presented the highest antioxidant capacities for black mulberries, blackberries and strawberries, respectively. Antioxidants extractions are extremely affected by the solvent combination used. In addition, the obtained extracts with the organic solvent-water mixtures were distinguished from the extracts obtained with pure organic solvents, through the PCA analysis.

Can green solvents be alternatives for thermal stabilization of collagen?

PubMed

Mehta, Ami; Rao, J Raghava; Fathima, Nishter Nishad

2014-08-01

"Go Green" campaign is gaining light for various industrial applications where water consumption needs to be reduced. To resolve this, industries have adopted usage of green, organic solvents, as an alternative to water. For leather making, tanning industry consumes gallons of water. Therefore, for adopting green solvents in leather making, it is necessary to evaluate its influence on type I collagen, the major protein present in the skin matrix. The thermal stability of collagen from rat tail tendon fiber (RTT) treated with seven green solvents namely, ethanol, ethyl lactate, ethyl acetate, propylene carbonate, propylene glycol, polyethylene glycol-200 and heptane was determined using differential scanning calorimetry (DSC). Crosslinking efficiency of basic chromium sulfate and wattle on RTT in green solvents was determined. DSC thermograms show increase in thermal stability of RTT collagen against heat with green solvents (>78°C) compared to water (63°C). In the presence of crosslinkers, RTT demonstrated thermal stability >100°C in some green solvents, resulting in increased intermolecular forces between collagen, solvent and crosslinkers. The significant improvement in thermal stability of collagen potentiates the capability of green solvents as an alternative for water. Copyright © 2014 Elsevier B.V. All rights reserved.

To Keep or Not to Keep? The Question of Crystallographic Waters for Enzyme Simulations in Organic Solvent

PubMed Central

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

System and method for treatment of a flue gas

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

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

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

Super-hydrophobic fluorine containing aerogels

DOEpatents

Coronado, Paul R [Livermore, CA; Poco, John F [Livermore, CA; Hrubesh, Lawrence W [Pleasanton, CA

2007-05-01

An aerogel material with surfaces containing fluorine atoms which exhibits exceptional hydrophobicity, or the ability to repel liquid water. Hydrophobic aerogels are efficient absorbers of solvents from water. Solvents miscible with water are separated from it because the solvents are more volatile than water and they enter the porous aerogel as a vapor across the liquid water/solid interface. Solvents that are immisicble with water are separated from it by selectively wetting the aerogel. The hydrophobic property is achieved by formulating the aerogel using fluorine containing molecules either directly by addition in the sol-gel process, or by treating a standard dried aerogel using the vapor of fluorine containing molecules.

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

PubMed Central

Brusseau, Mark L.; Narter, Matthew

2014-01-01

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

The Denaturation Transition of DNA in Mixed Solvents

PubMed Central

Hammouda, Boualem; Worcester, David

2006-01-01

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

Sleep disturbances and exposure to organic solvents

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

Lindelof, B.; Almkvist, O.; Goethe, C.

An inquiry about sleep habits and sleep disturbances revealed a significantly higher prevalence of insomnia in a solvent-exposed group than in a comparable group that had no occupational exposure to organic solvents. The solvent-exposed group has also registered an increased consumption of hypnotics, and a significant increase occurred in the number of individuals who had consulted physicians because of sleep disorders. The results indicate that solvent exposure could induce sleep disturbances.

Effect of reduced use of organic solvents on disability pension in painters.

PubMed

Järvholm, Bengt; Burdorf, Alex

2017-11-01

To investigate whether the decreased use of paints based on organic solvents has caused a decreased risk for neuropsychiatric disorders in painters by studying their incidence in disability pensions. The incidence of disability pension in Swedish painters who had participated in health examinations between 1971 and 1993 was studied through linkage with Swedish registers of disability pension over 1971-2010 and compared with the incidence in other construction workers as woodworkers, concrete workers and platers. When phasing out began in the 1970s, about 40% of paints were based on organic solvents and it had decreased to 4% in 1990s. The analysis was adjusted for age, time period, body mass index and smoking. The painters (n=23 065) had an increased risk of disability pension due to neurological diagnosis (n=285, relative risk (RR) 1.92, 95% CI 1.67 to 2.20) and psychiatric diagnosis (n=632, RR=1.61, 95 % CI 1.42 to 1.82). For neurological disorders there was a time trend with a continuously decreasing risk from 1980 onwards, but there was no such trend for psychiatric disorders. High exposure to organic solvents increased the risk for disability pension in neurological disorders, and the risk decreased when the use of organic solvents decreased. The painters also had an increased risk of disability pension due to psychiatric disorders, but the causes have to be further investigated. © Article author(s) (or their employer(s) unless otherwise stated in the text of the article) 2017. All rights reserved. No commercial use is permitted unless otherwise expressly granted.

On the relation between Marcus theory and ultrafast spectroscopy of solvation kinetics

NASA Astrophysics Data System (ADS)

Roy, Santanu; Galib, Mirza; Schenter, Gregory K.; Mundy, Christopher J.

2018-01-01

The phenomena of solvent exchange control the process of solvating ions, protons, and charged molecules. Building upon our extension of Marcus' philosophy of electron transfer, we provide a new perspective of ultrafast solvent exchange mechanism around ions measurable by two-dimensional infrared (2DIR) spectroscopy. In this theory, solvent rearrangement drives an ion-bound water to an activated state of higher coordination number, triggering ion-water separation that leads to the solvent-bound state of the water molecule. This ion-bound to solvent-bound transition rate for a BF4--water system is computed using ab initio molecular dynamics and Marcus theory, and is found to be in excellent agreement with the 2DIR measurement.

Water as a Solvent for Life

NASA Technical Reports Server (NTRS)

Pohorille, Andrew; Pratt, Lawrence R.

2015-01-01

"Follow the water" is our basic strategy in searching for life in the universe. The universality of water as the solvent for living systems is usually justified by arguing that water supports the rich organic chemistry that seeds life, but alternative chemistries are possible in other organic solvents. Here, other, essential criteria for life that have not been sufficiently considered so far, will be discussed.

Field comparison of thermal and non-thermal ultra-low-volume applications using water and diesel as solvents for managing dengue vector, Aedes aegypti.

PubMed

Harburguer, Laura; Lucia, Alejandro; Licastro, Susana; Zerba, Eduardo; Masuh, Héctor

2012-10-01

To compare the effectiveness on Aedes aegypti (Linneo) (Diptera: Culicidae) of a larvicide-adulticide ULV formulation applied by a thermal or a cold fogger using different solvents. We applied, in field conditions, a ULV formulation containing pyriproxyfen and permethrin, using a thermal and a cold fogger and water or diesel as solvent. We determined the effectiveness of these applications on Ae. aegypti adults and larvae by different bioassays and measuring Breteau, house and adult indices. When water was used as solvent, the treatments applied with the cold or the thermal foggers were equally effective on adult mortality (close to 90%) and adult emergence inhibition (% EI) (close to 70%). When the thermal fogger was used with water as solvent, the adult mortality outside the houses (85%) was higher, but not significantly different, than with diesel (65%). The contrary happens inside (22%vs. 58%), while there were no differences in %EI. Adult and larval indices behaved similarly in all areas, with a slight tendency for the treatments applied using water as solvent to be more effective. Water-based formulations are equally or more effective than the one applied with diesel as solvent. The use of water as solvent will not only improve the effectiveness of this formulation but also reduce the environmental impact and costs of spraying compared to the use of diesel. © 2012 Blackwell Publishing Ltd.

Process for removing halogenated aliphatic and aromatic compounds from petroleum products

DOEpatents

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

1983-09-20

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

Process for removing halogenated aliphatic and aromatic compounds from petroleum products

DOEpatents

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

1983-01-01

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

Optimization of soy isoflavone extraction with different solvents using the simplex-centroid mixture design.

PubMed

Yoshiara, Luciane Yuri; Madeira, Tiago Bervelieri; Delaroza, Fernanda; da Silva, Josemeyre Bonifácio; Ida, Elza Iouko

2012-12-01

The objective of this study was to optimize the extraction of different isoflavone forms (glycosidic, malonyl-glycosidic, aglycone and total) from defatted cotyledon soy flour using the simplex-centroid experimental design with four solvents of varying polarity (water, acetone, ethanol and acetonitrile). The obtained extracts were then analysed by high-performance liquid chromatography. The profile of the different soy isoflavones forms varied with different extractions solvents. Varying the solvent or mixture used, the extraction of different isoflavones was optimized using the centroid-simplex mixture design. The special cubic model best fitted to the four solvents and its combination for soy isoflavones extraction. For glycosidic isoflavones extraction, the polar ternary mixture (water, acetone and acetonitrile) achieved the best extraction; malonyl-glycosidic forms were better extracted with mixtures of water, acetone and ethanol. Aglycone isoflavones, water and acetone mixture were best extracted and total isoflavones, the best solvents were ternary mixture of water, acetone and ethanol.

On the relation between Marcus theory and ultrafast spectroscopy of solvation kinetics

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

Roy, Santanu; Galib, Mirza; Schenter, Gregory K.

The phenomena of solvent exchange control the process of solvating ions, protons, and charged molecules. Building upon our extension of Marcus’ philosophy of electron transfer, here we provide a new perspective of ultrafast solvent exchange mechanism around ions measurable by two-dimensional infrared (2DIR) spectroscopy. In this theory, solvent rearrangement drives an ion-bound water to an activated state of higher coordination number, triggering ion-water separation that leads to the solvent-bound state of the water molecule. This ion-bound to solvent-bound transition rate for a BF 4 --water system is then computed using ab initio molecular dynamics and Marcus theory, and is foundmore » to be in excellent agreement with the 2DIR measurement.« less

On the relation between Marcus theory and ultrafast spectroscopy of solvation kinetics

DOE PAGES

Roy, Santanu; Galib, Mirza; Schenter, Gregory K.; ...

2017-12-24

The phenomena of solvent exchange control the process of solvating ions, protons, and charged molecules. Building upon our extension of Marcus’ philosophy of electron transfer, here we provide a new perspective of ultrafast solvent exchange mechanism around ions measurable by two-dimensional infrared (2DIR) spectroscopy. In this theory, solvent rearrangement drives an ion-bound water to an activated state of higher coordination number, triggering ion-water separation that leads to the solvent-bound state of the water molecule. This ion-bound to solvent-bound transition rate for a BF 4 --water system is then computed using ab initio molecular dynamics and Marcus theory, and is foundmore » to be in excellent agreement with the 2DIR measurement.« less

On the relation between Marcus theory and ultrafast spectroscopy of solvation kinetics

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

Roy, Santanu; Galib, Mirza; Schenter, Gregory K.

The phenomena of solvent exchange control the process of solvating ions, protons, and charged molecules. Building upon our extension of Marcus’ philosophy of electron transfer, we provide a new perspective of ultrafast solvent exchange mechanism around ions measurable by two-dimensional infrared (2DIR) spectroscopy. In this theory, solvent rearrangement drives an ion-bound water to an activated state of higher coordination number, triggering ion-water separation that leads to the solvent-bound state of the water molecule. This ion-bound to solvent-bound transition rate for a BF4- water system is computed using ab initio molecular dynamics and Marcus theory, and is found to be inmore » excellent agreement with the 2DIR measurement.« less

A technique for determining the deuterium/hydrogen contrast map in neutron macromolecular crystallography.

PubMed

Chatake, Toshiyuki; Fujiwara, Satoru

2016-01-01

A difference in the neutron scattering length between hydrogen and deuterium leads to a high density contrast in neutron Fourier maps. In this study, a technique for determining the deuterium/hydrogen (D/H) contrast map in neutron macromolecular crystallography is developed and evaluated using ribonuclease A. The contrast map between the D2O-solvent and H2O-solvent crystals is calculated in real space, rather than in reciprocal space as performed in previous neutron D/H contrast crystallography. The present technique can thus utilize all of the amplitudes of the neutron structure factors for both D2O-solvent and H2O-solvent crystals. The neutron D/H contrast maps clearly demonstrate the powerful detectability of H/D exchange in proteins. In fact, alternative protonation states and alternative conformations of hydroxyl groups are observed at medium resolution (1.8 Å). Moreover, water molecules can be categorized into three types according to their tendency towards rotational disorder. These results directly indicate improvement in the neutron crystal structure analysis. This technique is suitable for incorporation into the standard structure-determination process used in neutron protein crystallography; consequently, more precise and efficient determination of the D-atom positions is possible using a combination of this D/H contrast technique and standard neutron structure-determination protocols.

Study of polymorphic control in an ethanol-water binary solvent

NASA Astrophysics Data System (ADS)

Kitano, Hiroshi; Tanaka, Takayuki; Hirasawa, Izumi

2017-07-01

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

Interaction-component analysis of the hydration and urea effects on cytochrome c

NASA Astrophysics Data System (ADS)

Yamamori, Yu; Ishizuka, Ryosuke; Karino, Yasuhito; Sakuraba, Shun; Matubayasi, Nobuyuki

2016-02-01

Energetics was analyzed for cytochrome c in pure-water solvent and in a urea-water mixed solvent to elucidate the solvation effect in the structural variation of the protein. The solvation free energy was computed through all-atom molecular dynamics simulation combined with the solution theory in the energy representation, and its correlations were examined over sets of protein structures against the electrostatic and van der Waals components in the average interaction energy of the protein with the solvent and the excluded-volume component in the solvation free energy. It was observed in pure-water solvent that the solvation free energy varies in parallel to the electrostatic component with minor roles played by the van der Waals and excluded-volume components. The effect of urea on protein structure was then investigated in terms of the free-energy change upon transfer of the protein solute from pure-water solvent to the urea-water mixed solvent. The decomposition of the transfer free energy into the contributions from urea and water showed that the urea contribution is partially canceled by the water contribution and governs the total free energy of transfer. When correlated against the change in the solute-solvent interaction energy upon transfer and the corresponding changes in the electrostatic, van der Waals, and excluded-volume components, the transfer free energy exhibited strong correlations with the total change in the solute-solvent energy and its van der Waals component. The solute-solvent energy was decomposed into the contributions from the protein backbone and side chain, furthermore, and neither of the contributions was seen to be decisive in the correlation to the transfer free energy.

Protein dynamics in organic media at varying water activity studied by molecular dynamics simulation.

PubMed

Wedberg, Rasmus; Abildskov, Jens; Peters, Günther H

2012-03-01

In nonaqueous enzymology, control of enzyme hydration is commonly approached by fixing the thermodynamic water activity of the medium. In this work, we present a strategy for evaluating the water activity in molecular dynamics simulations of proteins in water/organic solvent mixtures. The method relies on determining the water content of the bulk phase and uses a combination of Kirkwood-Buff theory and free energy calculations to determine corresponding activity coefficients. We apply the method in a molecular dynamics study of Candida antarctica lipase B in pure water and the organic solvents methanol, tert-butyl alcohol, methyl tert-butyl ether, and hexane, each mixture at five different water activities. It is shown that similar water activity yields similar enzyme hydration in the different solvents. However, both solvent and water activity are shown to have profound effects on enzyme structure and flexibility.

Solvent Effects of Model Polymeric Corrosion Control Coatings on Water Transport and Corrosion Rate

NASA Astrophysics Data System (ADS)

Konecki, Christina

Industrial coating formulations are often made for volatile organic content compliance and ease of application, with little regard for the solvent impact on resultant performance characteristics. Our research objective was to understand the effect of both solvent retention and chemical structure on water transport through polymer films and resultant corrosion area growth of coated steel substrates. A clear, unpigmented Phenoxy(TM) thermoplastic polymer (PKHH) was formulated into resin solutions with three separate solvent blends selected by Hansen solubility parameter (HSP), boiling point, and ability to solubilize PKHH. Polymer films cast from MEK/PGME (methyl ethyl ketone/ propylene glycol methyl ether), dried under ambient conditions (AMB, > 6wt.% residual solvent) produced a porous morphology, which resulted in a corrosion area greater than 50%. We attributed this to the water-soluble solvent used in film preparation, which enabled residual PGME to be extracted by water. The resin solution prepared with CYCOH/DXL (Cyclohexanol/ 1,3 dioxolane) was selected because CYCOH is a solid at room temperature which acts as a pigment in the final film. Therefore, increasing the tortuosity of water transport, as well as a high hydrogen bonding character, which caused more interactions with water, slowing diffusion, producing a nodular morphology, and 37% less corrosion area than MEK/PGME AMB. The HSP of PKHH and EEP (ethyl 3-ethoxypropionate) are within 5% of each other, which produced a homogeneous morphology and resulted in comparable corrosion rates regardless of residual solvent content. We utilized electrochemical techniques and attenuated total reflectance- Fourier transform infrared spectroscopy to elucidate dynamic water absorption and solvent extraction in the exposed model formulations. We found that water absorption resulted in a loss of barrier properties, and increased corrosion due to the voids formed by solvent extraction. The polymer films were rejuvenated (removal of water) as an attempt to decrease the number of water transport pathways during exposure. Results found that samples rejuvenated at temperatures above the glass transition temperature of the samples achieved lower moisture content and consequently, lower corrosion growth rates. In commercial systems, rejuvenation lowered the corrosion rate up to 60% indicating better coating formulations and maintenance cycles would control the corrosion rate.

Neutron structure of human carbonic anhydrase II in complex with methazolamide: Mapping the solvent and hydrogen-bonding patterns of an effective clinical drug

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

Aggarwal, Mayank; Kovalevsky, Andrey Y.; Velazquez, Hector

Carbonic anhydrases (CAs; EC 4.2.1.1) catalyze the interconversion of CO 2 and HCO 3 –, and their inhibitors have long been used as diuretics and as a therapeutic treatment for many disorders such as glaucoma and epilepsy. Acetazolamide (AZM) and methazolamide (MZM, a methyl derivative of AZM) are two of the classical CA inhibitory drugs that have been used clinically for decades. The jointly refined X-ray/neutron structure of MZM in complex with human CA isoform II (hCA II) has been determined to a resolution of 2.2 Å with an R cryst of ~16.0%. Presented in this article, along with onlymore » the second neutron structure of a clinical drug-bound hCA, is an in-depth structural comparison and analyses of differences in hydrogen-bonding network, water-molecule orientation and solvent displacement that take place upon the binding of AZM and MZM in the active site of hCA II. Even though MZM is slightly more hydrophobic and displaces more waters than AZM, the overall binding affinity ( K i) for both of the drugs against hCA II is similar (~10 n M). The plausible reasons behind this finding have also been discussed using molecular dynamics and X-ray crystal structures of hCA II–MZM determined at cryotemperature and room temperature. Furthermore, this study not only allows a direct comparison of the hydrogen bonding, protonation states and solvent orientation/displacement of AZM and MZM, but also shows the significant effect that the methyl derivative has on the solvent organization in the hCA II active site.« less

Neutron structure of human carbonic anhydrase II in complex with methazolamide: Mapping the solvent and hydrogen-bonding patterns of an effective clinical drug

DOE PAGES

Aggarwal, Mayank; Kovalevsky, Andrey Y.; Velazquez, Hector; ...

2016-07-22

Carbonic anhydrases (CAs; EC 4.2.1.1) catalyze the interconversion of CO 2 and HCO 3 –, and their inhibitors have long been used as diuretics and as a therapeutic treatment for many disorders such as glaucoma and epilepsy. Acetazolamide (AZM) and methazolamide (MZM, a methyl derivative of AZM) are two of the classical CA inhibitory drugs that have been used clinically for decades. The jointly refined X-ray/neutron structure of MZM in complex with human CA isoform II (hCA II) has been determined to a resolution of 2.2 Å with an R cryst of ~16.0%. Presented in this article, along with onlymore » the second neutron structure of a clinical drug-bound hCA, is an in-depth structural comparison and analyses of differences in hydrogen-bonding network, water-molecule orientation and solvent displacement that take place upon the binding of AZM and MZM in the active site of hCA II. Even though MZM is slightly more hydrophobic and displaces more waters than AZM, the overall binding affinity ( K i) for both of the drugs against hCA II is similar (~10 n M). The plausible reasons behind this finding have also been discussed using molecular dynamics and X-ray crystal structures of hCA II–MZM determined at cryotemperature and room temperature. Furthermore, this study not only allows a direct comparison of the hydrogen bonding, protonation states and solvent orientation/displacement of AZM and MZM, but also shows the significant effect that the methyl derivative has on the solvent organization in the hCA II active site.« less

Diazido­bis(5,5′-dimethyl-2,2′-bipyridyl-κ2 N,N′)nickel(II) monohydrate

PubMed Central

Phatchimkun, Jaturong; Kongsaeree, Palangpon; Suchaichit, Nattawut; Chaichit, Narongsak

2009-01-01

In the crystal structure of the title compound, [Ni(N3)2(C12H12N2)2]·H2O, the NiII atom is situated on a twofold axis and adopts a distorted octa­hedral geometry with the two 5,5′-dimethyl-2,2′-bipyridyl (dmbpy) and the two azide ligands in a cis arrangement. The water solvent mol­ecule is disordered over two positions in a 1:1 ratio. PMID:21577389

High-repetition-rate, narrow-band dye lasers with water as a solvent for dyes

NASA Astrophysics Data System (ADS)

Ray, Alok K.; Sinha, Sucharita; Kundu, Soumitra; Kumar, Sasi; Nair, Sivagiriyal Karunakaran Sreenivasan; Pal, Tamal; Dasgupta, Kamalesh

2002-03-01

The performance of a copper vapor laser-pumped narrow-band dye laser in oscillator-amplifier configuration with water-based binary mixture solvents is described. Although oscillator efficiency in water-surfactant (sodium lauryl sulfate) solvent was comparable with that that employed pure ethanolic solvent, amplifier efficiency was found to be lower. Experiments that were carried out with vertically polarized pump beams and either horizontally or vertically polarized signal beams show that, in case of both the pump and signal having orthogonal polarization (horizontal) and same polarization (vertical), the extraction efficiency for both ethanolic and water-micelle media increased substantially from 15.7% to 18.5% and from 10% to 12.5%, respectively. However, the relative difference remained nearly the same, indicating that a slower orientational diffusion of excited dye molecules in a micellar medium is not responsible for a decrease in amplifier efficiency. Amplifier efficiency comparable with that containing ethanolic dye solutions could be obtained with a binary solvent that comprises a mixture of water and about 30% n-propanol. The performances of two efficient dyes, Rhodamine-6G and Kiton Red S, using water-based solvents were studied.

Organosolv extraction of lignin from hydrolyzed almond shells and application of the delta-value theory.

PubMed

Quesada-Medina, Joaquín; López-Cremades, Francisco Javier; Olivares-Carrillo, Pilar

2010-11-01

The solubility of lignin from hydrolyzed almond (Prunus amygdalus) shells in different acetone, ethanol and dioxane-water mixtures and conditions (extraction time and temperature) was studied. The concept of the solubility parameter (delta-value) was applied to explain the effect of organic solvent concentration on lignin solubility. The organic solvent-water mixture that led to the highest lignin extraction was composed of a 75% vol. of organic solvent for all the solvent series investigated (acetone, ethanol and dioxane). Moreover, the best lignin extraction conditions were a temperature of 210 degrees C and an extraction time of 40 min for the acetone and ethanol series, and 25 min for the dioxane series. The delta-value of the hydrolyzed almond shell lignin [14.60 (cal/cm(3))(1/2)] and that of the organic solvent-water mixtures was calculated. The experimental delignification capacity of the aqueous organic solvents clearly reflected the proximity of their delta-value to that of lignin. The hydrogen-bonding capacity of the solvent-water mixtures was also taken into account. Copyright 2010 Elsevier Ltd. All rights reserved.

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

PubMed

Oshima, Hiraku; Kinoshita, Masahiro

2015-04-14

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

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

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

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

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

Continuous extraction of organic materials from water

USGS Publications Warehouse

Goldberg, M.C.; DeLong, L.; Kahn, L.

1971-01-01

A continuous liquid solvent extractor, designed to utilize organic solvents that are heavier than water, is described. The extractor is capable of handling input rates up to 2 liters per hour and has a 500-ml. extractant capacity. Extraction efficiency is dependent upon the p-value, the two solvent ratios, rate of flow of the aqueous phase, and rate of reflux of the organic phase. Extractors can be serially coupled to increase extraction efficiency and, when coupled with a lighter-than-water extractor, the system will allow the use of any immiscible solvent.

Droplet-Based Production of Liposomes

NASA Technical Reports Server (NTRS)

Ackley, Donald E.; Forster, Anita

2009-01-01

A process for making monodisperse liposomes having lipid bilayer membranes involves fewer, simpler process steps than do related prior methods. First, a microfluidic, cross junction droplet generator is used to produce vesicles comprising aqueous solution droplets contained in single layer lipid membranes. The vesicles are collected in a lipid-solvent mix that is at most partially soluble in water and is less dense than is water. A layer of water is dispensed on top of the solvent. By virtue of the difference in densities, the water sinks to the bottom and the solvent floats to the top. The vesicles, which have almost the same density as that of water, become exchanged into the water instead of floating to the top. As there are excess lipids in the solvent solution, in order for the vesicles to remain in the water, the addition of a second lipid layer to each vesicle is energetically favored. The resulting lipid bilayers present the hydrophilic ends of the lipid molecules to both the inner and outer membrane surfaces. If lipids of a second kind are dissolved in the solvent in sufficient excess before use, then asymmetric liposomes may be formed.

Impact of swelling characteristics on the permselective ...

EPA Pesticide Factsheets

The removal of water from organic solvents and biofuels, including lower alcohols (i.e., methanol, ethanol, propanol, and butanol), is necessary for the production, blending, and reuse of those organic compounds. Water forms an azeotrope with many hydrophilic solvents, complicating the separation of water/solvent mixtures. The use of water-selective membranes in a pervaporation or vapor permeation process enables the removal of water from the solvents, even when an azeotrope is present. Common hydrophilic polymer membranes often swell in water, resulting in permeabilities and selectivities that are dependent on the water content of the feed mixture. Recent work has shown the benefit of overcoating a hydrophilic water-permselective membrane with a non-swelling perfluoropolymer film [1,2]. The perfluoropolymer layer reduces the activity of water the hydrophilic polymer layer experiences, thereby reducing swelling in that layer and increasing the water selectivity of the multi-layer membrane relative to the selectivity of the base hydrophilic polymer, usually at the expense of permeability. In this work, the effect of overcoating the hydrophilic layer with polymer films of various swelling characteristics was modelled. Top layers that swell in the solvent offer some advantages, particularly with regard to the water permeance of the multi-layer composite. 1. Huang, Y.; Baker, R. W.; Wijmans, J. G. Perfluoro-coated hydrophilic membranes with improved selectivity. In

Polysaccharide structures and interactions in a lithium chloride/urea/water solvent.

PubMed

Winkworth-Smith, Charles G; MacNaughtan, William; Foster, Tim J

2016-09-20

The molten salt hydrate, lithium chloride (LiCl)/urea/water has previously been shown to swell cellulose, but there has so far been no work done to explore its effect on other polysaccharides. In this paper we have investigated the solvent effects of LiCl/urea/water on four natural polysaccharides. Fenugreek gum and xyloglucan, which are both highly branched, were found to increase in viscosity in LiCl/urea/water relative to water, possibly due to the breakage of all intra-molecular associations whereas the viscosity of konjac glucomannan which is predominantly unbranched did not change. Locust bean gum (LBG) had a lower viscosity in LiCl/urea/water compared to water due to the disruption of aggregates. Confocal microscopy showed that fenugreek gum and LBG are able to bind to cellulose in water, however, the conformational change of fenugreek gum in these solvent conditions inhibited it from binding to cellulose in LiCl/urea/water whereas conformational change allowed xyloglucan to bind to cellulose in LiCl/urea/water whilst it was unable to bind in water. Konjac glucomannan did not bind to cellulose in either solvent system. These results provide new insights into the impact of polysaccharide fine structure on conformational change in different solvent environments. Crown Copyright © 2016. Published by Elsevier Ltd. All rights reserved.

From benzos to berries: treatment offered at an Aboriginal youth solvent abuse treatment centre relays the importance of culture.

PubMed

Dell, Colleen Anne; Seguin, Maureen; Hopkins, Carol; Tempier, Raymond; Mehl-Madrona, Lewis; Dell, Debra; Duncan, Randy; Mosier, Karen

2011-02-01

First Nations and Inuit youth who abuse solvents are one of the most highly stigmatized substance-abusing groups in Canada. Drawing on a residential treatment response that is grounded in a culture-based model of resiliency, this article discusses the cultural implications for psychiatry's individualized approach to treating mental disorders. A systematic review of articles published in The Canadian Journal of Psychiatry during the past decade, augmented with a review of Canadian and international literature, revealed a gap in understanding and practice between Western psychiatric disorder-based and Aboriginal culture-based approaches to treatment and healing from substance abuse and mental disorders. Differing conceptualizations of mental health and substance abuse are discussed from Western psychiatric and Aboriginal worldviews, with a focus on connection to self, community, and political context. Applying an Aboriginal method of knowledge translation-storytelling-experiences from front-line workers in a youth solvent abuse treatment centre relay the difficulties with applying Western responses to Aboriginal healing. This lends to a discussion of how psychiatry can capitalize on the growing debate regarding the role of culture in the treatment of Aboriginal youth who abuse solvents. There is significant need for culturally competent psychiatric research specific to diagnosing and treating First Nations and Inuit youth who abuse substances, including solvents. Such understanding for front-line psychiatrists is necessary to improve practice. A health promotion perspective may be a valuable beginning point for attaining this understanding, as it situates psychiatry's approach to treating mental disorders within the etiology for Aboriginal Peoples.

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

DOE PAGES

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

2012-09-08

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

Water-enhanced solvation of organic solutes in ketone and ester solvents

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

Lee, J.H.; Brunt, V. van; King, C.J.

1994-05-01

Previous research has shown that the solubilities of dicarboxylic acids in certain electron-donor solvents are substantially increased in the presence of water. Information on solubilities, liquid-liquid equilibria and maximum-boiling ternary azeotropes was screened so as to identify other systems where codissolved water appears to enhance solvation of organic solutes in solvents. Several carboxylic acids, an alcohol, diols, and phenols were selected for examination as solutes in ketone and ester solvents. Effects of water upon solute solubilities and volatilities were measured. Results showed that water-enhanced solvation is greatest for carboxylic acids. Solute activity coefficients decreased by factors of 2--3, 6--8, andmore » 7--10 due to the presence of water for mono-, di and tricarboxylic acids, respectively. Activity coefficients decreased by a factor of about 1.5 for ethanol and 1,2-propanediol as solutes. Water-enhanced solvation of phenols is small, when existent.« less

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

NASA Astrophysics Data System (ADS)

Chandrasekaran, Neelakandan; Kyu, Thein

2008-03-01

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

Effects of solvent evaporation on water sorption/solubility and nanoleakage of adhesive systems.

PubMed

Chimeli, Talita Baumgratz Cachapuz; D'Alpino, Paulo Henrique Perlatti; Pereira, Patrícia Nóbrega; Hilgert, Leandro Augusto; Di Hipólito, Vinicius; Garcia, Fernanda Cristina Pimentel

2014-01-01

To evaluate the influence of solvent evaporation in the kinetics of water diffusion (water sorption-WS, solubility-SL, and net water uptake) and nanoleakage of adhesive systems. Disk-shaped specimens (5.0 mm in diameter x 0.8 mm in thickness) were produced (N=48) using the adhesives: Clearfil S3 Bond (CS3)/Kuraray, Clearfil SE Bond - control group (CSE)/Kuraray, Optibond Solo Plus (OS)/Kerr and Scotchbond Universal Adhesive (SBU)/3M ESPE. The solvents were either evaporated for 30 s or not evaporated (N=24/per group), and then photoactivated for 80 s (550 mW/cm2). After desiccation, the specimens were weighed and stored in distilled water (N=12) or mineral oil (N=12) to evaluate the water diffusion over a 7-day period. Net water uptake (%) was also calculated as the sum of WS and SL. Data were submitted to 3-way ANOVA/Tukey's test (α=5%). The nanoleakage expression in three additional specimens per group was also evaluated after ammoniacal silver impregnation after 7 days of water storage under SEM. Statistical analysis revealed that only the factor "adhesive" was significant (p<0.05). Solvent evaporation had no influence in the WS and SL of the adhesives. CSE (control) presented significantly lower net uptake (5.4%). The nanoleakage was enhanced by the presence of solvent in the adhesives. Although the evaporation has no effect in the kinetics of water diffusion, the nanoleakage expression of the adhesives tested increases when the solvents are not evaporated.

Direct and quantitative analysis of underivatized acylcarnitines in serum and whole blood using paper spray mass spectrometry

PubMed Central

Yang, Qian; Manicke, Nicholas E.; Wang, He; Petucci, Christopher; Cooks, R. Graham

2013-01-01

A simple protocol for rapid quantitation of acylcarnitines in serum and whole blood has been developed using paper spray mass spectrometry. Dried serum and whole blood containing a mixture of ten acylcarnitines at various concentrations were analyzed as spots from paper directly without any sample pretreatment, separation, or derivatization. The composition of the spray solvent was found to be a critical factor: for serum samples, spray solvent of methanol/water/formic acid (80:20:0.1) gave the best signal intensity while for blood samples which contain more matrix components, acetonitrile/water (90:10) was a much more suitable spray solvent. For the paper type and size used, 0.5 μL of sample provided an optimal signal for both serum and whole blood samples. For quantitative profiling, the limits of quantitation obtained from both serum and blood were much lower than the clinically validated cutoff values for diagnosis of fatty acid oxidation disorders in newborn screening. Linearity (R2>0.95) and reproducibility (RSD ~10 %) were achieved in the concentration ranges from 100 nM to 5 μM for the C2 acylcarnitine, and for other acylcarnitines, these values were from 10 to 500 nM. Acylcarnitine profiles offer an effective demonstration of the fact that paper spray mass spectrometry is an appropriate, simple, rapid method with high sensitivity and high reproducibility applicable to newborn screening tests. PMID:22760507

Solvent effects on enzymes - Implications for extraterrestrial life.

NASA Technical Reports Server (NTRS)

Heinrich, M. R.

1972-01-01

Review of several studies on the alterations taking place in the structure, catalytic activity, specificity, and stability of an enzyme when some or all of the water in the medium is replaced by another solvent. These studies show the utility of solvents as a tool for probing enzyme function. They also suggest that solvents other than water should be investigated as media for controlling and directing enzyme reactions.

Tris(1,10-phenanthroline-κ2 N,N′)nickel(II) hexa­oxido-μ-peroxido-disulfate­(VI) N,N-dimethyl­formamide disolvate monohydrate

PubMed Central

Harvey, Miguel Angel; Suarez, Sebastián; Doctorovich, Fabio; Baggio, Ricardo

2013-01-01

The asymmetric unit of the title complex, [Ni(C12H8N2)3]S2O8·2C3H7NO·H2O, consists of a complex [Ni(phen)3]2+ cation and one isolated pds anion, with two DMF mol­ecules and one water mol­ecule as solvates (where phen is 1,10-phenanthroline, pds is the hexa­oxido-μ-peroxoido-di­sulf­ate dianion and DMF is dimethyl­formamide). The [Ni(phen)3]2+ cation is regular, with an almost ideal NiII bond-valence sum of 2.07 v.u. The group, as well as the water solvent mol­ecule, are well behaved in terms of crystallographic order, but the remaining three mol­ecules in the structure display different kinds of disorder, viz. the two DMF mol­ecules mimic a twofold splitting and the pds anion has both S atoms clamped at well-determined positions but with a not-too-well-defined central part. These peculiar behaviours are a consequence of the hydrogen-bonding inter­actions: the outermost SO3 parts of the pds anion are heavily connected to the complex cations via C—H⋯O hydrogen bonding, generating an [Ni(phen)3]pds network and providing for the stability of the terminal pds sites. Also, the water solvent mol­ecule is strongly bound to the structure (being a donor of two strong bonds and an acceptor of one) and is accordingly perfectly ordered. The peroxide O atoms in the pds middle region, instead, appear as much less restrained into their sites, which may explain their tendency to disorder. The cation–anion network leaves large embedded holes, amounting to about 28% of the total crystal volume, which are occupied by the DMF mol­ecules. The latter are weakly inter­acting with the rest of the structure, which renders them much more labile and, accordingly, prone to disorder. PMID:23476355

Water equivalence of NIPAM based polymer gel dosimeters with enhanced sensitivity for x-ray CT

NASA Astrophysics Data System (ADS)

Gorjiara, Tina; Hill, Robin; Bosi, Stephen; Kuncic, Zdenka; Baldock, Clive

2013-10-01

Two new formulations of N-isopropylacrylamide (NIPAM) based three dimensional (3D) gel dosimeters have recently been developed with improved sensitivity to x-ray CT readout, one without any co-solvent and the other one with isopropanol co-solvent. The water equivalence of the NIPAM gel dosimeters was investigated using different methods to calculate their radiological properties including: density, electron density, number of electrons per grams, effective atomic number, photon interaction probabilities, mass attenuation and energy absorption coefficients, electron collisional, radiative and total mass stopping powers and electron mass scattering power. Monte Carlo modelling was also used to compare the dose response of these gel dosimeters with water for kilovoltage and megavoltage x-ray beams and for megavoltage electron beams. We found that the density and electron density of the co-solvent free gel dosimeter are more water equivalent with less than a 2.6% difference compared to a 5.7% difference for the isopropanol gel dosimeter. Both the co-solvent free and isopropanol solvent gel dosimeters have lower effective atomic numbers than water, differing by 2.2% and 6.5%, respectively. As a result, their photoelectric absorption interaction probabilities are up to 6% and 19% different from water, respectively. Compton scattering and pair production interaction probabilities of NIPAM gel with isopropanol differ by up to 10% from water while for the co-solvent free gel, the differences are 3%. Mass attenuation and energy absorption coefficients of the co-solvent free gel dosimeter and the isopropanol gel dosimeter are up to 7% and 19% lower than water, respectively. Collisional and total mass stopping powers of both gel dosimeters differ by less than 2% from those of water. The dose response of the co-solvent free gel dosimeter is water equivalent (with <1% discrepancy) for dosimetry of x-rays with energies <100 keV while the discrepancy increases (up to 5%) for the isopropanol gel dosimeter over the same energy range. For x-ray beams over the energy range 180 keV-18 MV, both gel dosimeters have less than 2% discrepancy with water. For megavoltage electron beams, the dose differences with water reach 7% and 14% for the co-solvent free gel dosimeter and the isopropanol gel dosimeter, respectively. Our results demonstrate that for x-ray beam dosimetry with photon energies higher than 100 keV and megavoltage electron beams, correction factors are needed for both NIPAM gels to be used as water equivalent dosimeters.

A Flemion-based actuator with ionic liquid as solvent

NASA Astrophysics Data System (ADS)

Wang, Jin; Xu, Chunye; Taya, Minoru; Kuga, Yasuo

2007-04-01

A perfluorinated carboxylic acid membrane, i.e. Flemion, shows improved performance as actuator material compared with Nafion (perfluorinated sulfonic acid). Flemion has a higher ion exchange capacity and good mechanical strength. In particular, Flemion will deform with no back relaxation under applied electrical stimulus. However, with water as solvent, the operation of Flemion in air has serious problems, since water would evaporate quickly in air. Moreover, the electrochemical stability for use in water is around 1 V at room temperature. In previous work, investigations on Nafion with ionic liquid as solvents have been carried out by some researchers and good results have been obtained. In this work, we explore the use of highly stable ionic liquid instead of water as solvent in Flemion. Experimental results indicate that Flemion-based actuators with ionic liquid as solvent have improved stability as compared to the water samples. Although the forces exhibited by Flemion-based actuators with the use of ionic liquid decreased dramatically compared to water, these preliminary results suggest good potential for the use of Flemion with ionic liquid in future applications.

Flemion-based actuator with ionic liquid as solvent

NASA Astrophysics Data System (ADS)

Wang, Jin; Xu, Chunye; Taya, Minoru; Kuga, Yasuo

2006-03-01

A perfluorinated carboxylic acid membrane, i.e. Flemion, shows improved performance as actuator material compared with Nafion (perfluorinated sulfonic acide). Flemion has a higher ion exchange capacity and good mechanical strength. Especially, Flemion will deform with no back relaxation when applied electrical stimulus. However, with water as solvent, the operation of Flemion in air has serious problems. Since water would evaporate quickly in air. Moreover, the electrochemical stability for use in water is around 1V at room temperature. In previous work, investigations on Nafion with ionic liquid as solvents have been carried out and good results have been obtained. In this work, we explore the use of highly stable ionic liquid instead of water as solvent in Flemion. Experimental results indicate that Flemion based actuators with ionic liquid as solvent have improved stability as compared to the water samples. Although the forces exhibited by Flemion based actuators with the use of ionic liquid decreased dramatically as compared to water, these preliminary results suggest a good potential for use of Flemion with ionic liquid in some applications.

Measurements of volatile compound contents in resins using a moisture analyzer.

PubMed

Hashimoto, Masanori; Nagano, Futami; Endo, Kazuhiko; Ohno, Hiroki

2010-02-01

The contents of volatile adhesive compounds, such as water, solvents, and residual unpolymerized monomers, affect the integrity and durability of adhesive bonding. However, there is no method available that can be used to rapidly assess the residual solvent or water contents of adhesive resins. This study examined the effectiveness of a digital moisture analyzer to measure the volatile compound contents of resins. Five self-etching adhesives and seven experimental light-cured resins prepared with different contents (0, 10, and 20% by weight) of water or solvents (acetone and ethanol) were examined in this study. The resins were prepared using different methods (with and without air blast or light-curing) to simulate the clinical conditions of adhesive application. Resin weight changes (% of weight loss) were determined as the residual volatile compound contents, using the moisture analyzer. After the measurements, the resin films were examined using a scanning electron microscope. The weight changes of the resins were found to depend on the amount of water or solvents evaporating from the resin. Water and solvents were evaporated by air blast or light-curing, but some of the water and solvents remained in the cured resin. The moisture analyzer is easy to operate and is a useful instrument for using to measure the residual volatile compound contents of adhesive resin.

Surface interactions between silica particles and water and organic solvents

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

Douillard, J.M.; Elwafir, M.; Partyka, S.

1994-04-01

A silica sample has been studied by vapor adsorption and by microcalorimetric methods. The combination of these two methods in the case of water allows one to calculate all the thermodynamic terms related to the adhesion on this silica. Adhesion between silica and miscellaneous solvents has been studied by immersion microcalorimetry. The silica is slightly hydrophobic, but the enthalpy of immersion into water is the most energetic one of all the solvents studied. It appears a clear graduation of the enthalpies of immersion due to the presence of delocalized electrons in the studied solvents.

Evaluation of the influence of the internal aqueous solvent structure on electrostatic interactions at the protein-solvent interface by nonlocal continuum electrostatic approach.

PubMed

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.

Synthesis of porous Cu-BTC with ultrasonic treatment: Effects of ultrasonic power and solvent condition.

PubMed

Israr, Farrukh; Kim, Duk Kyung; Kim, Yeongmin; Oh, Seung Jin; Ng, Kim Choon; Chun, Wongee

2016-03-01

Cu-BTC (BTC=1,3,5-benzenetricarboxylate) metal organic framework (MOF) was synthesized using different solvent conditions with ultrasonic treatment. Solvent mixtures of water/N,N-dimethylformamide (DMF), water/ethanol were used for the reactions with or without a variety of bases under 20 kHz ultrasonically treated conditions. Prepared crystals were purified through 30 min of sonication to remove unreacted chemicals. Treatment time and ultrasonic power effects were compared to get optimum synthetic condition. The characterization of MOF powders was performed by scanning electron microscopy, X-ray powder diffraction, infrared-spectroscopy, thermo-gravimetric analysis and specific surface determination using the BET method. Isolated crystal yields varied with different solvent and applied ultrasonic power conditions. A high isolated crystal yield of 86% was obtained from water/ethanol/DMF solvent system after 120 min of ultrasonic treatment at 40% power of 750 W. Different solvent conditions led to the formation of Cu-BTC with different surface area, and an extremely high surface area of 1430 m(2)/g was obtained from the crystals taken with the solvent condition of water:DMF=70:30. Copyright © 2015 Elsevier B.V. All rights reserved.

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

DOE PAGES

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

2016-04-27

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

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

NASA Astrophysics Data System (ADS)

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

2016-04-01

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

Improving the industrial production of 6-APA: enzymatic hydrolysis of penicillin G in the presence of organic solvents.

PubMed

Abian, Olga; Mateo, César; Fernández-Lorente, Gloria; Guisán, José M; Fernández-Lafuente, Roberto

2003-01-01

The hydrolysis of penicillin G in the presence of an organic solvent, used with the purpose of extracting it from the culture medium, may greatly simplify the industrial preparation of 6-APA. However, under these conditions, PGA immobilized onto Eupergit displays very low stability (half-life of 5 h in butanone-saturated water) and a significant degree of inhibition by the organic solvent (30%). The negative effect of the organic solvent strongly depended on the type of solvent utilized: water saturated with butanone (around 28% v/v) had a much more pronounced negative effect than that of methylisobutyl ketone (MIBK) (solubility in water was only 2%). These problems were sorted out by using a new penicillin G acylase derivative designed to work in the presence of organic solvents (with each enzyme molecule surrounded by an hydrophilic artificial environment) and a suitable organic solvent (MIBK). Using such solvent, this derivative kept its activity unaltered for 1 week at 32 degrees C. Moreover, the enzyme activity was hardly inhibited by the presence of the organic solvent. In this way, the new enzyme derivative thus prepared enables simplification of the industrial hydrolysis of penicillin G.

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

The solvent dependent shift of the amide I band of a fully solvated peptide in methanol/water mixtures as a local probe for the solvent composition in the peptide/solvent interface

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

Gnanakaran, S

2008-01-01

We determine the shift and line-shape of the amide I band of a model AK-peptide from molecular dynamics (MD) simulations of the peptide dissolved in methanol/water mixtures with varying composition. The IR-spectra are determined from a transition dipole coupling exciton model. A simplified empirical model Hamiltonian is employed, taking both the effect of hydrogen bonding, as well as intramolecular vibrational coupling into account. We consider a single isolated AK-peptide in a mostly helical conformation, while the solvent is represented by 2600 methanol or water molecules, simulated for a pressure of 1 bar and a temperature of 300 K. Over themore » course of the simulations minor reversible conformational changes at the termini are observed, which are found to only slightly affect the calculated spectral properties. Over the entire composition range, varying from pure water to the pure methanol solvent, a monotonous blue-shift of the IR amide I band of about 8 wavenumbers is observed. The shift is found to be caused by two counter-compensating effects: An intramolecular red-shift of about 1.2 wavenumbers, due to stronger intramolecular hydrogen-bonding in a methanol-rich environment. Dominating, however, is the intermolecular solvent-dependent blue-shift of about 10 wavenumbers, being attributed to the less effective hydrogen bond donor capabilities of methanol compared to water. The importance of solvent-contribution to the IR-shift, as well as the significantly different hydrogen formation capabilities of water and methanol make the amide I band sensitive to composition changes in the local environment close the peptide/solvent interface. This allows, in principle, an experimental determination of the composition of the solvent in close proximity to the peptide surface. For the AK-peptide case they observe at low methanol concentrations a significantly enhanced methanol concentration at the peptide/solvent-interface, supposedly promoted by the partially hydrophobic character of the AK-peptide's solvent accessible surface.« less

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

PubMed

Pourmohammadbagher, Amin; Shaw, John M

2015-09-15

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

Preparation of Water-Selective Polybutadiene Membranes and Their Use in Drying Alcohols by Pervaporation and Vapor Permeation Technologies

EPA Science Inventory

Separating azeotrope-forming solvent-water mixtures by conventional distillation poses technical, economic, and environmental challenges. Membrane technology using water-permselective membranes provides an efficient alternative for water removal from solvents. We present here a n...

Synthesis and characterization of low viscosity carbon dioxide binding organic liquids for flue gas clean up

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

Koech, Phillip K.; Malhotra, Deepika; Heldebrant, David J.

2015-01-01

Climate change is partly attributed to global anthropogenic carbon dioxide (CO2) emission to the atmosphere. These environmental effects can be mitigated by CO2 capture, utilization and storage. Alkanolamine solvents, such as monoethanolamine (MEA), which bind CO2 as carbamates or bicarbonate salts are used for CO2 capture in niche applications. These solvents consist of approximately 30 wt% of MEA in water, exhibiting a low, CO2-rich viscosity, fast kinetics and favorable thermodynamics. However, these solvents have low CO2 capacity and high heat capacity of water, resulting in prohibitively high costs of thermal solvent regeneration. Effective capture of the enormous amounts of CO2more » produced by coal-fired plants requires a material with high CO2 capacity and low regeneration energy requirements. To this end, several water-lean transformational solvents systems have been developed in order to reduce these energy penalties. These technologies include nano-material organic hybrids (NOHMs), task-specific, protic and conventional ionic liquids, phase change solvents. As part of an ongoing program in our group, we have developed new water lean transformational solvents known as CO2 binding organic liquids (CO2BOLs) which have the potential to be energy efficient CO2 capture solvents. These solvents, also known as switchable ionic liquids meaning, are organic solvents that can reversibly transform from non- ionic to ionic form and back. The zwitterionic state in these liquids is formed when low polarity non-ionic alkanolguanidines or alkanolamidines react with CO2 or SO2 to form ionic liquids with high polarity. These polar ionic liquids can be thermally converted to the less polar non-ionic solvent by releasing CO2.« less

Halogenated solvent remediation

DOEpatents

Sorenson, Jr., Kent S.

2008-11-11

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

Effects of solvent evaporation on water sorption/solubility and nanoleakage of adhesive systems

PubMed Central

CHIMELI, Talita Baumgratz Cachapuz; D'ALPINO, Paulo Henrique Perlatti; PEREIRA, Patrícia Nóbrega; HILGERT, Leandro Augusto; DI HIPÓLITO, Vinicius; GARCIA, Fernanda Cristina Pimentel

2014-01-01

Objective To evaluate the influence of solvent evaporation in the kinetics of water diffusion (water sorption-WS, solubility-SL, and net water uptake) and nanoleakage of adhesive systems. Material and Methods Disk-shaped specimens (5.0 mm in diameter x 0.8 mm in thickness) were produced (N=48) using the adhesives: Clearfil S3 Bond (CS3)/Kuraray, Clearfil SE Bond - control group (CSE)/Kuraray, Optibond Solo Plus (OS)/Kerr and Scotchbond Universal Adhesive (SBU)/3M ESPE. The solvents were either evaporated for 30 s or not evaporated (N=24/per group), and then photoactivated for 80 s (550 mW/cm2). After desiccation, the specimens were weighed and stored in distilled water (N=12) or mineral oil (N=12) to evaluate the water diffusion over a 7-day period. Net water uptake (%) was also calculated as the sum of WS and SL. Data were submitted to 3-way ANOVA/Tukey's test (α=5%). The nanoleakage expression in three additional specimens per group was also evaluated after ammoniacal silver impregnation after 7 days of water storage under SEM. Results Statistical analysis revealed that only the factor "adhesive" was significant (p<0.05). Solvent evaporation had no influence in the WS and SL of the adhesives. CSE (control) presented significantly lower net uptake (5.4%). The nanoleakage was enhanced by the presence of solvent in the adhesives. Conclusions Although the evaporation has no effect in the kinetics of water diffusion, the nanoleakage expression of the adhesives tested increases when the solvents are not evaporated. PMID:25141201

Dimensionality of Hallucinogen and Inhalant/Solvent Abuse and Dependence Criteria: Implications for the Diagnostic and Statistical Manual of Mental Disorders – Fifth Edition

PubMed Central

Kerridge, Bradley T.; Saha, Tulshi D.; Smith, Sharon; Chou, Patricia S.; Pickering, Roger P.; Huang, Boji; Ruan, June W.; Pulay, Attila J.

2012-01-01

Background Prior research has demonstrated the dimensionality of Diagnostic and Statistical Manual of Mental Disorders - Fourth Edition (DSM-IV) alcohol, nicotine, cannabis, cocaine and amphetamine abuse and dependence criteria. The purpose of this study was to examine the dimensionality of hallucinogen and inhalant/solvent abuse and dependence criteria. In addition, we assessed the impact of elimination of the legal problems abuse criterion on the information value of the aggregate abuse and dependence criteria, another proposed change for DSM- IV currently lacking empirical justification. Methods Factor analyses and item response theory (IRT) analyses were used to explore the unidimisionality and psychometric properties of hallucinogen and inhalant/solvent abuse and dependence criteria using a large representative sample of the United States (U.S.) general population. Results Hallucinogen and inhalant/solvent abuse and dependence criteria formed unidimensional latent traits. For both substances, IRT models without the legal problems abuse criterion demonstrated better fit than the corresponding model with the legal problem abuse criterion. Further, there were no differences in the information value of the IRT models with and without the legal problems abuse criterion, supporting the elimination of that criterion. No bias in the new diagnoses was observed by sex, age and race-ethnicity. Conclusion Consistent with findings for alcohol, nicotine, cannabis, cocaine and amphetamine abuse and dependence criteria, hallucinogen and inhalant/solvent criteria reflect underlying dimensions of severity. The legal problems criterion associated with each of these substance use disorders can be eliminated with no loss in informational value and an advantage of parsimony. Taken together, these findings support the changes to substance use disorder diagnoses recommended by the DSM-V Substance and Related Disorders Workgroup, that is, combining DSM-IV abuse and dependence criteria and eliminating the legal problems abuse criterion. PMID:21621334

Dimensionality of hallucinogen and inhalant/solvent abuse and dependence criteria: implications for the Diagnostic and Statistical Manual of Mental Disorders-Fifth Edition.

PubMed

Kerridge, Bradley T; Saha, Tulshi D; Smith, Sharon; Chou, Patricia S; Pickering, Roger P; Huang, Boji; Ruan, June W; Pulay, Attila J

2011-09-01

Prior research has demonstrated the dimensionality of Diagnostic and Statistical Manual of Mental Disorders-Fourth Edition (DSM-IV) alcohol, nicotine, cannabis, cocaine and amphetamine abuse and dependence criteria. The purpose of this study was to examine the dimensionality of hallucinogen and inhalant/solvent abuse and dependence criteria. In addition, we assessed the impact of elimination of the legal problems abuse criterion on the information value of the aggregate abuse and dependence criteria, another proposed change for DSM-IV currently lacking empirical justification. Factor analyses and item response theory (IRT) analyses were used to explore the unidimisionality and psychometric properties of hallucinogen and inhalant/solvent abuse and dependence criteria using a large representative sample of the United States (U.S.) general population. Hallucinogen and inhalant/solvent abuse and dependence criteria formed unidimensional latent traits. For both substances, IRT models without the legal problems abuse criterion demonstrated better fit than the corresponding model with the legal problem abuse criterion. Further, there were no differences in the information value of the IRT models with and without the legal problems abuse criterion, supporting the elimination of that criterion. No bias in the new diagnoses was observed by sex, age and race-ethnicity. Consistent with findings for alcohol, nicotine, cannabis, cocaine and amphetamine abuse and dependence criteria, hallucinogen and inhalant/solvent criteria reflect underlying dimensions of severity. The legal problems criterion associated with each of these substance use disorders can be eliminated with no loss in informational value and an advantage of parsimony. Taken together, these findings support the changes to substance use disorder diagnoses recommended by the DSM-V Substance and Related Disorders Workgroup, that is, combining DSM-IV abuse and dependence criteria and eliminating the legal problems abuse criterion. Published by Elsevier Ltd.

Structural and hydrodynamic properties of an intrinsically disordered region of a germ cell-specific protein on phase separation

PubMed Central

Brady, Jacob P.; Farber, Patrick J.; Sekhar, Ashok; Lin, Yi-Hsuan; Huang, Rui; Bah, Alaji; Chan, Hue Sun; Forman-Kay, Julie D.; Kay, Lewis E.

2017-01-01

Membrane encapsulation is frequently used by the cell to sequester biomolecules and compartmentalize their function. Cells also concentrate molecules into phase-separated protein or protein/nucleic acid “membraneless organelles” that regulate a host of biochemical processes. Here, we use solution NMR spectroscopy to study phase-separated droplets formed from the intrinsically disordered N-terminal 236 residues of the germ-granule protein Ddx4. We show that the protein within the concentrated phase of phase-separated Ddx4, Ddx4cond, diffuses as a particle of 600-nm hydrodynamic radius dissolved in water. However, NMR spectra reveal sharp resonances with chemical shifts showing Ddx4cond to be intrinsically disordered. Spin relaxation measurements indicate that the backbone amides of Ddx4cond have significant mobility, explaining why high-resolution spectra are observed, but motion is reduced compared with an equivalently concentrated nonphase-separating control. Observation of a network of interchain interactions, as established by NOE spectroscopy, shows the importance of Phe and Arg interactions in driving the phase separation of Ddx4, while the salt dependence of both low- and high-concentration regions of phase diagrams establishes an important role for electrostatic interactions. The diffusion of a series of small probes and the compact but disordered 4E binding protein 2 (4E-BP2) protein in Ddx4cond are explained by an excluded volume effect, similar to that found for globular protein solvents. No changes in structural propensities of 4E-BP2 dissolved in Ddx4cond are observed, while changes to DNA and RNA molecules have been reported, highlighting the diverse roles that proteinaceous solvents play in dictating the properties of dissolved solutes. PMID:28894006

Halogenated solvent remediation

DOEpatents

Sorenson, Kent S.

2004-08-31

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

Crystallization of perovskite film using ambient moisture and water as co-solvent for efficient planar perovskite solar cell (Conference Presentation)

NASA Astrophysics Data System (ADS)

Dubey, Ashish; Reza, Khan M.; Gaml, Eman; Adhikari, Nirmal; Qiao, Qiquan

2016-09-01

Smooth, compact and defect free morphology of perovskite is highly desired for enhanced device performance. Several routes such as thermal annealing, use of solvent mixtures, growth under controlled humidity has been adopted to obtain crystalline, smooth and defect free perovskite film. Herein we showed direct use of water (H2O) as co-solvent in precursor solution and have optimized the water content required to obtain smooth and dense film. Varying concentration of water was used in precursor solution of CH3NH3I and PbI2 mixed in γ-butyrolactone (GBL) and dimethylsulfoxide (DMSO). Perovskite films were crystallized using toluene assisted solvent engineering method using GBL:DMSO:H2O as solvent mixture. The amount of water was varied from 1% to 25%, which resulted in change in film morphology and perovskite crystallinity. It was concluded that an appropriate amount of water is required to assist the crystallization process to obtain smooth pin-hole free morphology. The change in morphology led to improved fill factor in the device, with highest efficiency 14%, which was significantly higher than devices made from perovskite film without adding water. We also showed that addition of up to 25% by volume of water does not significantly change the device performance.

Low-Temperature, Solution-Processed, Transparent Zinc Oxide-Based Thin-Film Transistors for Sensing Various Solvents.

PubMed

You, Hsin-Chiang; Wang, Cheng-Jyun

2017-02-26

A low temperature solution-processed thin-film transistor (TFT) using zinc oxide (ZnO) film as an exposed sensing semiconductor channel was fabricated to detect and identify various solution solvents. The TFT devices would offer applications for low-cost, rapid and highly compatible water-soluble detection and could replace conventional silicon field effect transistors (FETs) as bio-sensors. In this work, we demonstrate the utility of the TFT ZnO channel to sense various liquids, such as polar solvents (ethanol), non-polar solvents (toluene) and deionized (DI) water, which were dropped and adsorbed onto the channel. It is discussed how different dielectric constants of polar/non-polar solvents and DI water were associated with various charge transport properties, demonstrating the main detection mechanisms of the thin-film transistor.

Protein-solvent preferential interactions, protein hydration, and the modulation of biochemical reactions by solvent components.

PubMed

Timasheff, Serge N

2002-07-23

Solvent additives (cosolvents, osmolytes) modulate biochemical reactions if, during the course of the reaction, there is a change in preferential interactions of solvent components with the reacting system. Preferential interactions can be expressed in terms of preferential binding of the cosolvent or its preferential exclusion (preferential hydration). The driving force is the perturbation by the protein of the chemical potential of the cosolvent. It is shown that the measured change of the amount of water in contact with protein during the course of the reaction modulated by an osmolyte is a change in preferential hydration that is strictly a measure of the cosolvent chemical potential perturbation by the protein in the ternary water-protein-cosolvent system. It is not equal to the change in water of hydration, because water of hydration is a reflection strictly of protein-water forces in a binary system. There is no direct relation between water of preferential hydration and water of hydration.

Comparison of magnesium sulfate and sodium sulfate for removal of water from pesticide extracts of foods.

PubMed

Schenck, Frank J; Callery, Patrick; Gannett, Peter M; Daft, Jonathan R; Lehotay, Steven J

2002-01-01

Water-miscible solvents, such as acetone and acetonitrile, effectively extract both polar and nonpolar pesticide residues from nonfatty foods. The addition of sodium chloride to the resulting acetonitrile-water or acetone-water extract (salting out) results in the separation of the water from the organic solvent. However, the organic solvent layer (pesticide extract) still contains some residual water, which can adversely affect separation procedures that follow, such as solid-phase extraction and/or gas chromatography. Drying agents, such as sodium sulfate or magnesium sulfate, are used to remove the water from the organic extracts. In the present study, we used nuclear magnetic resonance spectroscopy to study the composition of the phases resulting from salting out and to compare the effectiveness of sodium sulfate and magnesium sulfate as drying agents. The study showed that considerable amounts of water remained in the organic phase after phase separation. Sodium sulfate was a relatively ineffective drying agent, removing little or no residual water from the organic solvent. Magnesium sulfate proved to be a much more effective drying agent.

Reference interaction site model with hydrophobicity induced density inhomogeneity: An analytical theory to compute solvation properties of large hydrophobic solutes in the mixture of polyatomic solvent molecules.

PubMed

Cao, Siqin; Sheong, Fu Kit; Huang, Xuhui

2015-08-07

Reference interaction site model (RISM) has recently become a popular approach in the study of thermodynamical and structural properties of the solvent around macromolecules. On the other hand, it was widely suggested that there exists water density depletion around large hydrophobic solutes (>1 nm), and this may pose a great challenge to the RISM theory. In this paper, we develop a new analytical theory, the Reference Interaction Site Model with Hydrophobicity induced density Inhomogeneity (RISM-HI), to compute solvent radial distribution function (RDF) around large hydrophobic solute in water as well as its mixture with other polyatomic organic solvents. To achieve this, we have explicitly considered the density inhomogeneity at the solute-solvent interface using the framework of the Yvon-Born-Green hierarchy, and the RISM theory is used to obtain the solute-solvent pair correlation. In order to efficiently solve the relevant equations while maintaining reasonable accuracy, we have also developed a new closure called the D2 closure. With this new theory, the solvent RDFs around a large hydrophobic particle in water and different water-acetonitrile mixtures could be computed, which agree well with the results of the molecular dynamics simulations. Furthermore, we show that our RISM-HI theory can also efficiently compute the solvation free energy of solute with a wide range of hydrophobicity in various water-acetonitrile solvent mixtures with a reasonable accuracy. We anticipate that our theory could be widely applied to compute the thermodynamic and structural properties for the solvation of hydrophobic solute.

Water's role in the force-induced unfolding of ubiquitin.

PubMed

Li, Jingyuan; Fernandez, Julio M; Berne, B J

2010-11-09

In atomic force spectroscopic studies of the elastomeric protein ubiquitin, the β-strands 1-5 serve as the force clamp. Simulations show how the rupture force in the force-induced unfolding depends on the kinetics of water molecule insertion into positions where they can eventually form hydrogen bonding bridges with the backbone hydrogen bonds in the force-clamp region. The intrusion of water into this region is slowed down by the hydrophobic shielding effect of carbonaceous groups on the surface residues of β-strands 1-5, which thereby regulates water insertion prior to hydrogen bond breakage. The experiments show that the unfolding of the mechanically stressed protein is nonexponential due to static disorder. Our simulations show that different numbers and/or locations of bridging water molecules give rise to a long-lived distribution of transition states and static disorder. We find that slowing down the translational (not rotational) motions of the water molecules by increasing the mass of their oxygen atoms, which leaves the force field and thereby the equilibrium structure of the solvent unchanged, increases the average rupture force; however, the early stages of the force versus time behavior are very similar for our "normal" and fictitious "heavy" water models. Finally, we construct six mutant systems to regulate the hydrophobic shielding effect of the surface residues in the force-clamp region. The mutations in the two termini of β-sheets 1-5 are found to determine a preference for different unfolding pathways and change mutant's average rupture force.

Solvent-induced dimensional changes in EDTA-demineralized dentin matrix.

PubMed

Pashley, D H; Agee, K A; Nakajima, M; Tay, F R; Carvalho, R M; Terada, R S; Harmon, F J; Lee, W K; Rueggeberg, F A

2001-08-01

The purpose of this study was to test the null hypothesis that the re-expansion of dried matrix and the shrinkage of moist, demineralized dentin is not influenced by polar solvents. Dentin disks were prepared from midcoronal dentin of extracted human third molars. After complete demineralization in 0.5M of EDTA (pH 7), the specimens were placed in the well of a device that measures changes in matrix height in real time. Dry, collapsed matrices were created by blowing dry N(2) on the specimens until they shrank to a stable plateau. Polar solvents [water, methanol, ethanol, n-propanol, n-butanol, formamide, ethylene glycol, hydroxyethyl methacrylate (HEMA), or mixtures of water-HEMA] as model primers then were added and the degree of re-expansion measured. These same solvents also were applied to moist, expanded matrices and the solvent-induced shrinkages measured. Regression analysis was used to test the correlations between matrix height and Hansen's dispersive, polar, hydrogen bonding, and total solubility parameters (delta(d), delta(p), delta(h), delta(t)). The results indicate that water-free polar solvents of low hydrogen bonding (H-bond) ability (e.g., neat HEMA) do not re-expand dried matrices and that they shrink moist matrices. When HEMA was mixed with progressively higher water concentrations, the model water-HEMA primers expanded the dried matrix in proportion to their water concentrations and they produced less shrinkage of moist matrices. Solvents with higher H-bonding capacities (methanol, ethanol, ethylene glycol, formamide, and water) re-expanded the dried matrix in proportion to their solubility parameters for H-bonding (delta(h)). They also induced small transient shrinkages of moist matrices, which slowly re-expanded. The results require rejection of the null hypothesis. Copyright 2001 John Wiley & Sons, Inc. J Biomed Mater Res 56: 273-281, 2001

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

DOE PAGES

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

2016-08-02

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

Technical and economic analysis of solvent-based lithium-ion electrode drying with water and NMP

DOE PAGES

Wood, David L.; Quass, Jeffrey D.; Li, Jianlin; ...

2017-05-16

Processing lithium-ion battery (LIB) electrode dispersions with water as the solvent during primary drying offers many advantages over N-methylpyrrolidone (NMP). An in-depth analysis of the comparative drying costs of LIB electrodes is discussed for both NMP- and water-based dispersion processing in terms of battery pack $/kWh. Electrode coating manufacturing and capital equipment cost savings are compared for water vs. conventional NMP organic solvent processing. A major finding of this work is that the total electrode manufacturing costs, whether water- or NMP-based, contribute about 8–9% of the total pack cost. However, it was found that up to a 2 × reductionmore » in electrode processing (drying and solvent recovery) cost can be expected along with a $3–6 M savings in associated plant capital equipment (for a plant producing 100,000 10-kWh Plug-in Hybrid Electric Vehicle (PHEV) batteries) using water as the electrode solvent. This paper shows a different perspective in that the most important benefits of aqueous electrode processing actually revolve around capital equipment savings and environmental stewardship and not processing cost savings.« less

A turn-on type stimuli-responsive fluorescent dye with specific solvent effect: Implication for a new prototype of paper using water as the ink

NASA Astrophysics Data System (ADS)

Hu, Xiaochen; Liu, Yang; Duan, Yuai; Han, Jingqi; Li, Zhongfeng; Han, Tianyu

2017-09-01

In this study, we reported the photoluminescence (PL) behaviour of a new intramolecular charge transfer (ICT) compound, ((E)-2-(((2-hydroxynaphthalen-1-yl)methylene)amino)benzoic acid, (HABA), which shows ICT solvent effect in aprotic solvents as confirmed by absorption and emission spectra. While in protic solvents including water and ethanol, the charge transfer (CT) band significantly reduces. Remarkable fluorescence enhancement in the blue region was also observed for HABA in polar protic solvents. We described such phenomena as ;specific solvent effect;. It can be ascribed to the hydrogen bonding formation between HABA and protic solvents, which not only causes significant reduction in the rate of internal conversion but also elevates the energy gap. Density functional theory (DFT) calculations as well as the dynamics analysis were performed to further verify the existence of hydrogen bonding complexes. Stronger emission turn-on effect was observed on HABA solid film when it is treated with water and base solution. The stimuli-responsive fluorescence of HABA enables a new green printing technique that uses water/base as the ink, affording fluorescent handwritings highly distinct from the background. Thermoanalysis of the dye suggests the nice thermostability, which is highly desired for real-world printing in a wide temperature range.

Microscopic relaxations in a protein sustained down to 160 K in a non-glass forming organic solvent

DOE PAGES

Mamontov, Eugene; O'Neil, Hugh

2016-05-03

In this paper, we have studied microscopic dynamics of a protein in carbon disulfide, a non-glass forming solvent, down to its freezing temperature of ca. 160 K. We have utilized quasielastic neutron scattering. A comparison of lysozyme hydrated with water and dissolved in carbon disulfide reveals a stark difference in the temperature dependence of the protein's microscopic relaxation dynamics induced by the solvent. In the case of hydration water, the common protein glass-forming solvent, the protein relaxation slows down in response to a large increase in the water viscosity on cooling down, exhibiting a well-known protein dynamical transition. The dynamicalmore » transition disappears in non-glass forming carbon disulfide, whose viscosity remains a weak function of temperature all the way down to freezing at just below 160 K. The microscopic relaxation dynamics of lysozyme dissolved in carbon disulfide is sustained down to the freezing temperature of its solvent at a rate similar to that measured at ambient temperature. Finally, our results demonstrate that protein dynamical transition is not merely solvent-assisted, but rather solvent-induced, or, more precisely, is a reflection of the temperature dependence of the solvent's glass-forming dynamics.« less

Empirical parameters for solvent acidity, basicity, dipolarity, and polarizability of the ionic liquids [BMIM][BF4] and [BMIM][PF6].

PubMed

del Valle, J C; García Blanco, F; Catalán, J

2015-04-02

The empirical solvent scales for polarizability (SP), dipolarity (SdP), acidity (SA), and basicity (SB) have been successfully used to interpret the solvatochromism of compounds dissolved in organic solvents and their solvent mixtures. Providing that the published solvatochromic parameters for the ionic liquids 1-(1-butyl)-3-methylimidazolium tetrafluoroborate, [BMIM][BF4] and 1-(1-butyl)-3-methylimidazolium hexafluorophosphate, [BMIM][PF6], are excessively widespread, their SP, SdP, SA, and SB values are measured herein at temperatures from 293 to 353 K. Four key points are emphasized herein: (i) the origin of the solvatochromic solvent scales--the gas phase, that is the absence of any medium perturbation--; (ii) the separation of the polarizability and dipolarity effects; (iii) the simplification of the probing process in order to obtain the solvatochromic parameters; and (iv) the SP, SdP, SA, and SB solvent scales can probe the polarizability, dipolarity, acidity, and basicity of ionic liquids as well as of organic solvents and water-organic solvent mixtures. From the multiparameter approach using the four pure solvent scales one can draw the conclusion that (a) the solvent influence of [BMIM][BF4] parallels that of formamide at 293 K, both of them miscible with water; (b) [BMIM][PF6] shows a set of solvatochromic parameters similar to that of chloroacetonitrile, both of them water insoluble; and (c) that the corresponding solvent acidity and basicity of the ionic liquids can be explained to a great extent from the cation species by comparing the empirical parameters of [BMIM](+) with those of the solvent 1-methylimidazole. The insolubility of [BMIM][PF6] in water as compared to [BMIM][BF4] is tentatively connected to some extent to the larger molar volume of the anion [PF6](-), and to the difference in basicity of [PF6](-) and [BF4](-).

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

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

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

2010-01-01

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

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

Mamontov, Eugene; O'Neil, Hugh

In this paper, we have studied microscopic dynamics of a protein in carbon disulfide, a non-glass forming solvent, down to its freezing temperature of ca. 160 K. We have utilized quasielastic neutron scattering. A comparison of lysozyme hydrated with water and dissolved in carbon disulfide reveals a stark difference in the temperature dependence of the protein's microscopic relaxation dynamics induced by the solvent. In the case of hydration water, the common protein glass-forming solvent, the protein relaxation slows down in response to a large increase in the water viscosity on cooling down, exhibiting a well-known protein dynamical transition. The dynamicalmore » transition disappears in non-glass forming carbon disulfide, whose viscosity remains a weak function of temperature all the way down to freezing at just below 160 K. The microscopic relaxation dynamics of lysozyme dissolved in carbon disulfide is sustained down to the freezing temperature of its solvent at a rate similar to that measured at ambient temperature. Finally, our results demonstrate that protein dynamical transition is not merely solvent-assisted, but rather solvent-induced, or, more precisely, is a reflection of the temperature dependence of the solvent's glass-forming dynamics.« less

Nonhazardous solvent composition and method for cleaning metal surfaces

DOEpatents

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.

Nonhazardous solvent composition and method for cleaning metal surfaces

DOEpatents

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.

Incorporation of the TIP4P water model into a continuum solvent for computing solvation free energy

NASA Astrophysics Data System (ADS)

Yang, Pei-Kun

2014-10-01

The continuum solvent model is one of the commonly used strategies to compute solvation free energy especially for large-scale conformational transitions such as protein folding or to calculate the binding affinity of protein-protein/ligand interactions. However, the dielectric polarization for computing solvation free energy from the continuum solvent is different than that obtained from molecular dynamic simulations. To mimic the dielectric polarization surrounding a solute in molecular dynamic simulations, the first-shell water molecules was modeled using a charge distribution of TIP4P in a hard sphere; the time-averaged charge distribution from the first-shell water molecules were estimated based on the coordination number of the solute, and the orientation distribution of the first-shell waters and the intermediate water molecules were treated as that of a bulk solvent. Based on this strategy, an equation describing the solvation free energy of ions was derived.

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

Cao, Siqin; Department of Chemistry, Hong Kong University of Science and Technology, Clear Water Bay, Kowloon; Sheong, Fu Kit

Reference interaction site model (RISM) has recently become a popular approach in the study of thermodynamical and structural properties of the solvent around macromolecules. On the other hand, it was widely suggested that there exists water density depletion around large hydrophobic solutes (>1 nm), and this may pose a great challenge to the RISM theory. In this paper, we develop a new analytical theory, the Reference Interaction Site Model with Hydrophobicity induced density Inhomogeneity (RISM-HI), to compute solvent radial distribution function (RDF) around large hydrophobic solute in water as well as its mixture with other polyatomic organic solvents. To achievemore » this, we have explicitly considered the density inhomogeneity at the solute-solvent interface using the framework of the Yvon-Born-Green hierarchy, and the RISM theory is used to obtain the solute-solvent pair correlation. In order to efficiently solve the relevant equations while maintaining reasonable accuracy, we have also developed a new closure called the D2 closure. With this new theory, the solvent RDFs around a large hydrophobic particle in water and different water-acetonitrile mixtures could be computed, which agree well with the results of the molecular dynamics simulations. Furthermore, we show that our RISM-HI theory can also efficiently compute the solvation free energy of solute with a wide range of hydrophobicity in various water-acetonitrile solvent mixtures with a reasonable accuracy. We anticipate that our theory could be widely applied to compute the thermodynamic and structural properties for the solvation of hydrophobic solute.« less

Theoretical analysis of co-solvent effect on the proton transfer reaction of glycine in a water-acetonitrile mixture

NASA Astrophysics Data System (ADS)

Kasai, Yukako; Yoshida, Norio; Nakano, Haruyuki

2015-05-01

The co-solvent effect on the proton transfer reaction of glycine in a water-acetonitrile mixture was examined using the reference interaction-site model self-consistent field theory. The free energy profiles of the proton transfer reaction of glycine between the carboxyl oxygen and amino nitrogen were computed in a water-acetonitrile mixture solvent at various molar fractions. Two types of reactions, the intramolecular proton transfer and water-mediated proton transfer, were considered. In both types of the reactions, a similar tendency was observed. In the pure water solvent, the zwitterionic form, where the carboxyl oxygen is deprotonated while the amino nitrogen is protonated, is more stable than the neutral form. The reaction free energy is -10.6 kcal mol-1. On the other hand, in the pure acetonitrile solvent, glycine takes only the neutral form. The reaction free energy from the neutral to zwitterionic form gradually increases with increasing acetonitrile concentration, and in an equally mixed solvent, the zwitterionic and neutral forms are almost isoenergetic, with a difference of only 0.3 kcal mol-1. The free energy component analysis based on the thermodynamic cycle of the reaction also revealed that the free energy change of the neutral form is insensitive to the change of solvent environment but the zwitterionic form shows drastic changes. In particular, the excess chemical potential, one of the components of the solvation free energy, is dominant and contributes to the stabilization of the zwitterionic form.

Low-Temperature, Solution-Processed, Transparent Zinc Oxide-Based Thin-Film Transistors for Sensing Various Solvents

PubMed Central

You, Hsin-Chiang; Wang, Cheng-Jyun

2017-01-01

A low temperature solution-processed thin-film transistor (TFT) using zinc oxide (ZnO) film as an exposed sensing semiconductor channel was fabricated to detect and identify various solution solvents. The TFT devices would offer applications for low-cost, rapid and highly compatible water-soluble detection and could replace conventional silicon field effect transistors (FETs) as bio-sensors. In this work, we demonstrate the utility of the TFT ZnO channel to sense various liquids, such as polar solvents (ethanol), non-polar solvents (toluene) and deionized (DI) water, which were dropped and adsorbed onto the channel. It is discussed how different dielectric constants of polar/non-polar solvents and DI water were associated with various charge transport properties, demonstrating the main detection mechanisms of the thin-film transistor. PMID:28772592

Study to find the best extraction solvent for use with guava leaves (Psidium guajava L.) for high antioxidant efficacy.

PubMed

Seo, Jongkwon; Lee, Soojung; Elam, Marcus L; Johnson, Sarah A; Kang, Jonghoon; Arjmandi, Bahram H

2014-03-01

The effects of guava leaves extracted using solvents of water, ethanol, methanol, and different concentrations of hydroethanolic solvents on phenolic compounds and flavonoids, and antioxidant properties have been investigated. The antioxidant capability was assessed based on 2,2-diphenyl-1-picrylhydrazyl radical and 2,2'-azinobis-(3-ethylbenzothiazoline-6-sulfonic acid) radical-scavenging abilities, reducing power, and nitric oxide-and nitrate-scavenging activities. The results demonstrated that the antioxidant ability of guava leaf extracts has a strong relationship with phenolic compound content rather than flavonoid content. Phenolic compound content of water extracted guava leaves was higher compared to pure ethanol and methanol extracts. However, phenolic compound content extracted using hydroethanolic solvent was higher than water, whereas 50% hydroethanolic was observed to be the most effective solvent showing high antioxidant ability.

Solubility of 3-Caffeoylquinic Acid in Different Solvents at 291-340 K

NASA Astrophysics Data System (ADS)

Wang, Y. T.; Zhang, C. L.; Cheng, X. L.; Zhao, J. H.; Wang, L. C.

2017-12-01

Using a laser monitoring observation technique the solubilities of 3-caffeoylquinic acid in pure solvents, water, methanol, ethanol, 1-propanol, 1-butanol, and two mixed solvents, methanol + water, ethanol + water have been determined at temperature range from 291-340 K. The experimental data were correlated by the modified Apelblat equation, λ h equation, and ideal model. The calculated solubilities were turned out very consistent with the experimental results, and the modified Apelblat equation shows the best agreement.

High-yield exfoliation of tungsten disulphide nanosheets by rational mixing of low-boiling-point solvents

NASA Astrophysics Data System (ADS)

Sajedi-Moghaddam, Ali; Saievar-Iranizad, Esmaiel

2018-01-01

Developing high-throughput, reliable, and facile approaches for producing atomically thin sheets of transition metal dichalcogenides is of great importance to pave the way for their use in real applications. Here, we report a highly promising route for exfoliating two-dimensional tungsten disulphide sheets by using binary combination of low-boiling-point solvents. Experimental results show significant dependence of exfoliation yield on the type of solvents as well as relative volume fraction of each solvent. The highest yield was found for appropriate combination of isopropanol/water (20 vol% isopropanol and 80 vol% water) which is approximately 7 times higher than that in pure isopropanol and 4 times higher than that in pure water. The dramatic increase in exfoliation yield can be attributed to perfect match between the surface tension of tungsten disulphide and binary solvent system. Furthermore, solvent molecular size also has a profound impact on the exfoliation efficiency, due to the steric repulsion.

Optimization of deep eutectic solvent-based ultrasound-assisted extraction of polysaccharides from Dioscorea opposita Thunb.

PubMed

Zhang, Lijin; Wang, Maoshan

2017-02-01

In this study, deep eutectic solvents were proposed for the ultrasound-assisted extraction of polysaccharides from Dioscorea opposita Thunb. Several deep eutectic solvents were prepared for the extraction of polysaccharides, among which the deep eutectic solvent composed of choline chloride and 1,4-butanediol was proved to be suitable for the extraction. Based on the screening of single-factor experiment design and orthogonal experiment design, three experimental factors were optimized for the Box-Behnken experimental design combined with response surface methodology, which gave the optimal extraction conditions: water content of 32.89%(v/v), extraction temperature of 94.00°C, and the extraction time of 44.74min. The optimal extraction conditions could supply higher extraction yield than those of hot water extraction and water-based ultrasound-assisted extraction. Therefore, deep eutectic solvents were an excellent extraction solvent alternative to the extraction of polysaccharides from sample matrices. Copyright © 2016 Elsevier B.V. All rights reserved.

Determination of water traces in various organic solvents using Karl Fischer method under FIA conditions.

PubMed

Dantan, N; Frenzel, W; Küppers, S

2000-05-31

Flow injection methods utilising the Karl Fischer (KF) reaction with spectrophotometric and potentiometric detection are described for the determination of the trace water content in various organic solvents. Optimisation of the methods resulted in an accessible (linear) working range of 0.01-0.2% water for many solvents studied with a typical precision of 1-2% R.S.D. Only 50 mul of organic solvent was injected and the sampling frequency was about 120 samples per h. Since the slopes of the calibration curves were different for different solvents appropriate calibration was required. Problems associated with spectrophotometric detection and caused by refractive index changes were pointed out and a nested-loop configuration was proposed to overcome this kind of interference. The potentiometric method with a novel flow-through detector cell was shown to surpass the performance of spectrophotometric detection in any respect. The characteristics of the procedures developed made them well applicable for on-line monitoring of technical solvent distillations in an industrial plant.

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)

Microreactor of Pd nanoparticles immobilized hollow microspheres for catalytic hydrodechlorination of chlorophenols in water.

PubMed

Lan, Yang; Yang, Li; Zhang, Minchao; Zhang, Wangqing; Wang, Shengnan

2010-01-01

A microreactor of Pd nanoparticles immobilized shell-corona hollow microspheres of poly[styrene-co-2-(acetoacetoxy) ethyl methacrylate-co-acrylamide] has been designed for catalytic hydrodechlorination (HDC) of chlorophenols in the sole solvent of water. The strategy of the combined use of the shell-corona hollow microspheres as microcapsule and catalyst scaffold endues the microreactor several advantages. First, the microreactor can be dispersed in the sole solvent of water and acts as a quasi-homogeneous catalyst for catalytic HDC of chlorophenols. Second, the reactant of chlorophenols can be highly concentrated within the hollow microspheres of the microreactor in the sole solvent of water. Third, the resultant product of phenol can be favorably excreted off the microreactor into water because of the polar difference between the reactant of chlorophenols and the product of phenol. Ascribed to the combined advantages, catalytic HDC of chlorophenols can be performed efficiently within the microreactor in the sole solvent of water at room temperature under atmosphere pressure.

Exceptional ion rejection ability of directional solvent for non-membrane desalination

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

Rish, Daniel; Department of Civil Engineering, University of Notre Dame, Notre Dame, Indiana 46556; Luo, Shirui

2014-01-13

The recently demonstrated directional solvent extraction (DSE) is promising for very low temperature, membrane-free water desalination. In this paper, we combine atomistic simulations and experimental validation to demonstrate that the currently used directional solvent, decanoic acid, can reject all major salt ions in seawater, with very high rejection rates. The salinities of the DSE recovered water show that ion rejection rates are ∼98%–99%—similar to those of the best reverse osmosis membranes. Our test also shows that the DSE process can desalt seawater to produce fresh water that meets drinking water standards.

Aqueous or solvent based surface modification: The influence of the combination solvent - organic functional group on the surface characteristics of titanium dioxide grafted with organophosphonic acids

NASA Astrophysics Data System (ADS)

Roevens, Annelore; Van Dijck, Jeroen G.; Geldof, Davy; Blockhuys, Frank; Prelot, Benedicte; Zajac, Jerzy; Meynen, Vera

2017-09-01

To alter the versatility of interactions at its surface, TiO2 is modified with organophosphonic acids (PA). A thorough understanding of the role of all synthesis conditions is necessary to achieve controlled functionalization. This study reports on the effect of using water, toluene and their mixtures when performing the modification of TiO2 with PA. Sorption and calorimetry measurements of surface interactions with various probing species clearly indicate that, by grafting PA in water, clear differences appear in the distribution of organic groups on the surface. Also the functional group of the PA determines the impact of using water as solvent. Modification in toluene results in a higher modification degree for propylphosphonic acid (3PA), as the solvent-solute interaction may hinder the grafting with phenylphosphonic acid (PhPA) in toluene. Water is preferred as solvent for PhPA modification as stabilizing π-OH interactions enhance surface grafting overcoming the competitive interaction of water at the surface as observed with 3PA. By using water in toluene mixtures for the functionalization of TiO2 with 3PA, the degree of functionalization is higher than when only water or toluene is used. Furthermore, adding small amounts of water leads to the formation of titanium propylphosphonates, next to surface grafting.

Spin-crossover in [Fe(3-bpp)2][BF4]2 in different solvents--a dramatic stabilisation of the low-spin state in water.

PubMed

Barrett, Simon A; Kilner, Colin A; Halcrow, Malcolm A

2011-12-07

The temperature of spin-crossover in [Fe(3-bpp)(2)][BF(4)](2) (3-bpp = 2,6-di{pyrazol-3-yl}pyridine) tends to increase in associating solvents. In particular, T(½) shifts to 60-70 K higher temperature in water compared to organic solvents.

Stereochemistry and solvent role in protein folding: nuclear magnetic resonance and molecular dynamics studies of poly-L and alternating-L,D homopolypeptides in dimethyl sulfoxide.

PubMed

Srivastava, Kinshuk Raj; Kumar, Anil; Goyal, Bhupesh; Durani, Susheel

2011-05-26

The competing interactions folding and unfolding protein structure remain obscure. Using homopolypeptides, we ask if poly-L structure may have a role. We mutate the structure to alternating-L,D stereochemistry and substitute water as the fold-promoting solvent with methanol and dimethyl sulfoxide (DMSO) as the fold-denaturing solvents. Circular dichroism and molecular dynamics established previously that, while both isomers were folded in water, the poly-L isomer was unfolded and alternating-L,D isomer folded in methanol. Nuclear magnetic resonance and molecular dynamics establish now that both isomers are unfolded in DMSO. We calculated energetics of folding-unfolding equilibrium with water and methanol as solvents. We have now calculated interactions of unfolded polypeptide structures with DMSO as solvent. Methanol was found to unfold and water fold poly-L structure as a dielectric. DMSO has now been found to unfold both poly-L and alternating-L,D structures by strong solvation of peptides to disrupt their hydrogen bonds. Accordingly, we propose that while linked peptides fold protein structure with hydrogen bonds they unfold the structure electrostatically due to the stereochemical effect of the poly-L structure. Protein folding to ordering of peptide hydrogen bonds with water as canonical solvent may thus involve two specific and independent solvent effects-one, strong screening of electrostatics of poly-L linked peptides, and two, weak dipolar solvation of peptides. Correspondingly, protein denaturation may involve two independent solvent effects-one, weak dielectric to unfold poly-L structure electrostatically, and two, strong polarity to disrupt peptide hydrogen bonds by solvation of peptides.

Molecular Dynamics Analysis of Lysozyme Protein in Ethanol-Water Mixed Solvent Environment

NASA Astrophysics Data System (ADS)

Ochije, Henry Ikechukwu

Effect of protein-solvent interaction on the protein structure is widely studied using both experimental and computational techniques. Despite such extensive studies molecular level understanding of proteins and some simple solvents is still not fully understood. This work focuses on detailed molecular dynamics simulations to study of solvent effect on lysozyme protein, using water, alcohol and different concentrations of water-alcohol mixtures as solvents. The lysozyme protein structure in water, alcohol and alcohol-water mixture (0-12% alcohol) was studied using GROMACS molecular dynamics simulation code. Compared to water environment, the lysozome structure showed remarkable changes in solvents with increasing alcohol concentration. In particular, significant changes were observed in the protein secondary structure involving alpha helices. The influence of alcohol on the lysozyme protein was investigated by studying thermodynamic and structural properties. With increasing ethanol concentration we observed a systematic increase in total energy, enthalpy, root mean square deviation (RMSD), and radius of gyration. a polynomial interpolation approach. Using the resulting polynomial equation, we could determine above quantities for any intermediate alcohol percentage. In order to validate this approach, we selected an intermediate ethanol percentage and carried out full MD simulation. The results from MD simulation were in reasonably good agreement with that obtained using polynomial approach. Hence, the polynomial approach based method proposed here eliminates the need for computationally intensive full MD analysis for the concentrations within the range (0-12%) studied in this work.

IR, Raman and Vibrational Optical Activity Spectra of Methyl Glycidate in Chloroform and Water: The Clusters-in-a-Liquid Solvation Model.

PubMed

Xu, Yunjie; Perera, Angelo Shehan; Cheramy, Joseph; Merten, Christian; Thomas, Javix

2018-05-16

Solvent effects, in particular those involving water as the solvent, are of significant interest to chemistry and physics communities. IR, vibrational circular dichroism (VCD), Raman, and Raman optical activity (ROA) spectra of methyl glycidate in two very different solvents, namely CCl4 and water, have been measured experimentally and simulated theoretically. While the observed spectra in CCl4 could be well modelled using the polarizable continuum model for the solvent, the situation is much different in water. The experimental VCD spectrum of methyl glycidate in water reveals strong induced VCD signatures in the water bending region, indicating the presence of the relatively long-lived methyl glycidate-watern complexes. We applied the clusters-in-a-liquid approach to identify the dominant methyl glycidate-water1,2 complexes which are the long-lived species responsible for all the spectra observed in water. We examined the influences of solvent dielectric environment and the hydrogen-bonding interactions on the conformational distribution of methyl glycidate. The geometry optimizations, frequency calculations, IR, VCD, Raman and ROA intensity calculations were performed at the B3LYP/6-311++G(2d,p) and aug-cc-pVTZ levels of theory with D3BJ dispersion correction. It is particularly satisfying to note that the clusters-in-a-liquid approach has captured all main experimental features in IR, VCD, Raman and ROA spectra of methyl glycidate in water. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Motor neuron disease and optic neuropathy after acute exposure to a methanol-containing solvent mixture.

PubMed

Chiò, Adriano; Herrero Hernandez, Elena; Mora, Gabriele; Valentini, Consuelo; Discalzi, Gianluigi; Pira, Enrico

2004-09-01

A 34-years-old floor-layer developed optic neuropathy and motor neuron disease after being accidentally exposed to a solvent mixture containing methanol and other substances. Optic neuropathy is a complication of methanol poisoning, but the onset of a motor neuron disorder resembling amyotrophic lateral sclerosis after the exposure to these substances has not been previously described. The temporal onset of the clinical symptoms, biological plausibility, young age of the patient and absence of neurological disorders in the family history raises suspicion of a possible causative relationship.

Pseudolatex preparation using a novel emulsion-diffusion process involving direct displacement of partially water-miscible solvents by distillation.

PubMed

Quintanar-Guerrero, D; Allémann, E; Fessi, H; Doelker, E

1999-10-25

Pseudolatexes were obtained by a new process based on an emulsification-diffusion technique involving partially water-miscible solvents. The preparation method consisted of emulsifying an organic solution of polymer (saturated with water) in an aqueous solution of a stabilizing agent (saturated with solvent) using conventional stirrers, followed by direct solvent distillation. The technique relies on the rapid displacement of the solvent from the internal into the external phase which thereby provokes polymer aggregation. Nanoparticle formation is believed to occur because rapid solvent diffusion produces regions of local supersaturation near the interface, and nanoparticles are formed due to the ensuing interfacial phase transformations and polymer aggregation that occur in these interfacial domains. Using this method, it was possible to prepare pseudolatexes of biodegradable and non-biodegradable polymers such as poly(D,L-lactic acid) and poly(epsilon-caprolactone), Eudragit E, cellulose acetate phthalate, cellulose acetate trimellitate using ethyl acetate or 2-butanone as partially water-miscible solvents and poly(vinyl alcohol) or poloxamer 407 as stabilizing agent. A transition from nano- to microparticles was observed at high polymer concentrations. At concentrations above 30% w/v of Eudragit E in ethyl acetate or cellulose acetate phthalate in 2-butanone only microparticles were obtained. This behaviour was attributed to decreased transport of polymer molecules into the aqueous phase.

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

NASA Astrophysics Data System (ADS)

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

2011-08-01

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

Study to find the best extraction solvent for use with guava leaves (Psidium guajava L.) for high antioxidant efficacy

PubMed Central

Seo, Jongkwon; Lee, Soojung; Elam, Marcus L; Johnson, Sarah A; Kang, Jonghoon; Arjmandi, Bahram H

2014-01-01

The effects of guava leaves extracted using solvents of water, ethanol, methanol, and different concentrations of hydroethanolic solvents on phenolic compounds and flavonoids, and antioxidant properties have been investigated. The antioxidant capability was assessed based on 2,2-diphenyl-1-picrylhydrazyl radical and 2,2′-azinobis-(3-ethylbenzothiazoline-6-sulfonic acid) radical-scavenging abilities, reducing power, and nitric oxide-and nitrate-scavenging activities. The results demonstrated that the antioxidant ability of guava leaf extracts has a strong relationship with phenolic compound content rather than flavonoid content. Phenolic compound content of water extracted guava leaves was higher compared to pure ethanol and methanol extracts. However, phenolic compound content extracted using hydroethanolic solvent was higher than water, whereas 50% hydroethanolic was observed to be the most effective solvent showing high antioxidant ability. PMID:24804076

Docking glycosaminoglycans to proteins: analysis of solvent inclusion

NASA Astrophysics Data System (ADS)

Samsonov, Sergey A.; Teyra, Joan; Pisabarro, M. Teresa

2011-05-01

Glycosaminoglycans (GAGs) are anionic polysaccharides, which participate in key processes in the extracellular matrix by interactions with protein targets. Due to their charged nature, accurate consideration of electrostatic and water-mediated interactions is indispensable for understanding GAGs binding properties. However, solvent is often overlooked in molecular recognition studies. Here we analyze the abundance of solvent in GAG-protein interfaces and investigate the challenges of adding explicit solvent in GAG-protein docking experiments. We observe PDB GAG-protein interfaces being significantly more hydrated than protein-protein interfaces. Furthermore, by applying molecular dynamics approaches we estimate that about half of GAG-protein interactions are water-mediated. With a dataset of eleven GAG-protein complexes we analyze how solvent inclusion affects Autodock 3, eHiTs, MOE and FlexX docking. We develop an approach to de novo place explicit solvent into the binding site prior to docking, which uses the GRID program to predict positions of waters and to locate possible areas of solvent displacement upon ligand binding. To investigate how solvent placement affects docking performance, we compare these results with those obtained by taking into account information about the solvent position in the crystal structure. In general, we observe that inclusion of solvent improves the results obtained with these methods. Our data show that Autodock 3 performs best, though it experiences difficulties to quantitatively reproduce experimental data on specificity of heparin/heparan sulfate disaccharides binding to IL-8. Our work highlights the current challenges of introducing solvent in protein-GAGs recognition studies, which is crucial for exploiting the full potential of these molecules for rational engineering.

Impact of swelling characteristics on the permselective properties of multi-layer composite membranes for water removal from alcohols.

EPA Science Inventory

The removal of water from organic solvents and biofuels, including lower alcohols (i.e., methanol, ethanol, propanol, and butanol), is necessary for the production, blending, and reuse of those organic compounds. Water forms an azeotrope with many hydrophilic solvents, complicati...

Solvent composition of one-step self-etch adhesives and dentine wettability.

PubMed

Grégoire, Geneviève; Dabsie, Firas; Dieng-Sarr, Farimata; Akon, Bernadette; Sharrock, Patrick

2011-01-01

Our aim was to determine the wettability of dentine by four commercial self-etch adhesives and evaluate their spreading rate on the dentine surface. Any correlation with chemical composition was sought, particularly with the amount of solvent or HEMA present in the adhesive. The adhesives used were AdheSE One, Optibond All.In.One, Adper Easy Bond and XenoV. Chemical compositions were determined by proton nuclear magnetic resonance (NMR) spectroscopy of the adhesives dissolved in dimethylsulfoxide. Apparent contact angles for sessile drops of adhesives were measured on dentine slices as a function of time for up to 180s. The water contact angles were determined for fully polymerised adhesives. All adhesives were water-based with total solvent contents ranging from 27% to 73% for HEMA-free adhesives, and averaging 45% for HEMA containing adhesives. The contents in hydrophobic groups decreased as water contents increased. No differences were found in the adhesive contact angles after 180s even though the spreading rates were different for the products tested. Water contact angles differed significantly but were not correlated with HEMA or solvent presence. Manufacturers use different approaches to stabilise acid co-monomer ingredients in self-etch adhesives. Co-solvents, HEMA, or acrylamides without co-solvents are used to simultaneously etch and infiltrate dentine. A large proportion of water is necessary for decalcification action. Copyright © 2010 Elsevier Ltd. All rights reserved.

The Role of Interfacial Water in Protein-Ligand Binding: Insights from the Indirect Solvent Mediated Potential of Mean Force.

PubMed

Cui, Di; Zhang, Bin W; Matubayasi, Nobuyuki; Levy, Ronald M

2018-02-13

Classical density functional theory (DFT) can be used to relate the thermodynamic properties of solutions to the indirect solvent mediated part of the solute-solvent potential of mean force (PMF). Standard, but powerful numerical methods can be used to estimate the solute-solvent PMF from which the indirect part can be extracted. In this work we show how knowledge of the direct and indirect parts of the solute-solvent PMF for water at the interface of a protein receptor can be used to gain insights about how to design tighter binding ligands. As we show, the indirect part of the solute-solvent PMF is equal to the sum of the 1-body (energy + entropy) terms in the inhomogeneous solvation theory (IST) expansion of the solvation free energy. To illustrate the effect of displacing interfacial water molecules with particular direct/indirect PMF signatures on the binding of ligands, we carry out simulations of protein binding with several pairs of congeneric ligands. We show that interfacial water locations that contribute favorably or unfavorably at the 1-body level (energy + entropy) to the solvation free energy of the solute can be targeted as part of the ligand design process. Water locations where the indirect PMF is larger in magnitude provide better targets for displacement when adding a functional group to a ligand core.

Hydrophilic organic/salt-containing aqueous two-phase solvent system for counter-current chromatography: a novel technique for separation of polar compounds.

PubMed

Liu, Dan; Zou, Xiaowei; Gao, Mingzhe; Gu, Ming; Xiao, Hongbin

2014-08-22

Hydrophilic organic/salt-containing aqueous two-phase system composing of ethanol, water and ammonium sulfate for separation polar compounds was investigated on multilayer coil associated with J-type HSCCC devices. Compared to the classical polar solvent system based on 1-butanol-water or PEG1000-ammonium sulfate-water, the water content of upper phase in ethanol-ammonium sulfate-water systems was from 53.7% to 32.8% (wt%), closed to PEG1000-ammonium sulfate-water aqueous two-phase systems and higher than 1-butanol-water (22.0%, wt%). Therefore, the polarity of ethanol-ammonium sulfate-water is in the middle of 1-butanol-water and PEG-ammonium sulfate-water system, which is quite good for separating polar compounds like phenols, nucleosides and amino acids with low partition coefficient in 1-octanol-water system. The retention of stationary phase in four elution mode on type-J counter-current chromatography devices with multilayer coil column changed from 26% to 71%. Hydrodynamic trend possess both intermediate and hydrophilic solvent system property, which closely related to the composition of solvent system. The applicability of this system was demonstrated by successful separation of adenosine, uridine guanosine and cytidine. Copyright © 2014 Elsevier B.V. All rights reserved.

Properties of Polyvinylpyrrolidone in a Deep Eutectic Solvent

DOE PAGES

Sapir, Liel; Stanley, Christopher B.; Harries, Daniel

2016-03-10

Deep eutectic solvents (DES) are mixtures of two or more components with high melting temperatures, which form a liquid at room temperature. These DES hold great promise as green solvents for chemical processes, as they are inexpensive and environmentally friendly. Specifically, they present a unique solvating environment to polymers that is different from water. In this paper, we use small angle neutron scattering to study the polymer properties of the common, water-soluble, polyvinylpyrrolidone (PVP) in the prominent DES formed by a 1:2 molar mixture of choline chloride and urea. We find that the polymer adopts a slightly different structure inmore » DES than in water, so that at higher concentrations the polymer favors a more expanded conformation compared to the same concentration in water. Yet, the osmotic pressure of PVP solutions in DES is very similar to that in water, indicating that both solvents are of comparable quality and that the DES components interact favorably with PVP. Finally, the osmotic pressure measurements within this novel class of promising solvents should be of value toward future technological applications as well as for osmotic stress experiments in nonaqueous environments.« less

Properties of Polyvinylpyrrolidone in a Deep Eutectic Solvent

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

Sapir, Liel; Stanley, Christopher B.; Harries, Daniel

Deep eutectic solvents (DES) are mixtures of two or more components with high melting temperatures, which form a liquid at room temperature. These DES hold great promise as green solvents for chemical processes, as they are inexpensive and environmentally friendly. Specifically, they present a unique solvating environment to polymers that is different from water. In this paper, we use small angle neutron scattering to study the polymer properties of the common, water-soluble, polyvinylpyrrolidone (PVP) in the prominent DES formed by a 1:2 molar mixture of choline chloride and urea. We find that the polymer adopts a slightly different structure inmore » DES than in water, so that at higher concentrations the polymer favors a more expanded conformation compared to the same concentration in water. Yet, the osmotic pressure of PVP solutions in DES is very similar to that in water, indicating that both solvents are of comparable quality and that the DES components interact favorably with PVP. Finally, the osmotic pressure measurements within this novel class of promising solvents should be of value toward future technological applications as well as for osmotic stress experiments in nonaqueous environments.« less

Hydrogen Bond Networks and Hydrophobic Effects in the Amyloid β30-35 Chain in Water: A Molecular Dynamics Study.

PubMed

Jong, KwangHyok; Grisanti, Luca; Hassanali, Ali

2017-07-24

We have studied the conformational landscape of the C-terminal fragment of the amyloid protein Aβ 30-35 in water using well-tempered metadynamics simulations and found that it resembles an intrinsically disordered protein. The conformational fluctuations of the protein are facilitated by a collective reorganization of both protein and water hydrogen bond networks, combined with electrostatic interactions between termini as well as hydrophobic interactions of the side chains. The stabilization of hydrophobic interactions in one of the conformers involves a collective collapse of the side chains along with a squeeze-out of water sandwiched between them. The charged N- and C-termini play a critical role in stabilizing different types of protein conformations, including those involving contact-ion salt bridges as well as solvent-mediated interactions of the termini and the amide backbone. We have examined this by probing the distribution of directed water wires forming the hydrogen bond network enveloping the polypeptide. Water wires and their fluctuations form an integral part of structural signature of the protein conformation.

Switchable hydrophilicity solvents for lipid extraction from microalgae for biofuel production.

PubMed

Boyd, Alaina R; Champagne, Pascale; McGinn, Patrick J; MacDougall, Karen M; Melanson, Jeremy E; Jessop, Philip G

2012-08-01

A switchable hydrophilicity solvent (SHS) was studied for its effectiveness at extracting lipids from freeze-dried samples of Botryococcus braunii microalgae. The SHS N,N-dimethylcyclohexylamine extracted up to 22 wt.% crude lipid relative to the freeze-dried cell weight. The solvent was removed from the extract with water saturated with carbon dioxide at atmospheric pressure and recovered from the water upon de-carbonation of the mixture. Liquid chromatography-mass spectrometry (LC-MS) showed that the extracted lipids contained high concentrations of long chain tri-, di- and mono-acylglycerols, no phospholipids, and only 4-8% of residual solvent. Unlike extractions with conventional organic solvents, this new method requires neither distillation nor the use of volatile, flammable or chlorinated organic solvents. Copyright © 2012 Elsevier Ltd. All rights reserved.

Extracting organic matter on Mars: A comparison of methods involving subcritical water, surfactant solutions and organic solvents

NASA Astrophysics Data System (ADS)

Luong, Duy; Court, Richard W.; Sims, Mark R.; Cullen, David C.; Sephton, Mark A.

2014-09-01

The first step in many life detection protocols on Mars involves attempts to extract or isolate organic matter from its mineral matrix. A number of extraction options are available and include heat and solvent assisted methods. Recent operations on Mars indicate that heating samples can cause the loss or obfuscation of organic signals from target materials, raising the importance of solvent-based systems for future missions. Several solvent types are available (e.g. organic solvents, surfactant based solvents and subcritical water extraction) but a comparison of their efficiencies in Mars relevant materials is missing. We have spiked the well characterised Mars analogue material JSC Mars-1 with a number of representative organic standards. Extraction of the spiked JSC Mars-1 with the three solvent methods provides insights into the relative efficiency of these methods and indicates how they may be used on future Mars missions.

Reutilization of mango byproducts: study of the effect of extraction solvent and temperature on their antioxidant properties.

PubMed

Dorta, Eva; Lobo, M Gloria; Gonzalez, Monica

2012-01-01

Mango biowastes, obtained after processing, contain large amounts of compounds with antioxidant activity that can be reused to reduce their environmental impact. The present study evaluates the effect of solvent (methanol, ethanol, acetone, water, methanol:water [1:1], ethanol:water [1:1], and acetone:water [1:1]), and temperature (25, 50, and 75 °C) on the efficiency of the extraction of antioxidants from mango peel and seed. Among the factors optimized, extraction solvent was the most important. The solvents that best obtained extracts with high antioxidant capacity were methanol, methanol:water, ethanol:water, and acetone:water (β-carotene test, antioxidant activity coefficient 173 to 926; thiobarbituric acid reactive substances test, inhibition ratio 15% to 89%; 2,2'-azino-bis-(3-ethylbenzothiazoline)-6-sulfonic acid ABTS(·+); and 2,2-diphenyl-1-picrylhydrazyl DPPH· scavenging, 7 to 22 and 8 to 28 g trolox equivalent antioxidant capacity [TE] per 100 g mango biowaste on a dry matter basis [DW]). Similarly, the flavonoid (0.21 to 1.4 g (+)-catechin equivalents per 100 g DW), tannin (3.8 to 14 g tannic acid equivalents per 100 g DW), and proanthocyanidin (0.23 to 7.8 g leucoanthocyanidin equivalents per 100 g DW) content was highest in the peel extracts obtained with methanol, ethanol:water, or acetone:water and in the seed extracts obtained with methanol or acetone:water. From the perspective of food security, it is advisable to choose ethanol (which also has a notable antioxidant content), ethanol:water, or acetone:water, as they are all solvents that can be used in compliance with good manufacturing practice. In general, increasing temperature improves the capacity of the extracts obtained from mango peel and seed to inhibit lipid peroxidation; however, its effect on the extraction of phytochemical compounds or on the capacity of the extracts to scavenge free radicals was negligible in comparison to that of the solvent. There are many antioxidant compounds in mango peel and seed, and they could be used as a natural and very inexpensive alternative to synthetic food additives. However, the conditions in which the antioxidants are extracted must be optimized. This work proves that conditions such as extraction solvent or temperature have a crucial impact on obtaining extracts rich in antioxidants from mango biowastes. © 2011 Institute of Food Technologists®

Process for enhancing the value of hydrocabonaceous natural recources

DOEpatents

Bunger, James W.; Cogswell, Donald E.

2005-04-05

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

Effects of concentration, temperature and solvent composition on density and apparent molar volume of the binary mixtures of cationic-anionic surfactants in methanol-water mixed solvent media.

PubMed

Bhattarai, Ajaya; Chatterjee, Sujeet Kumar; Niraula, Tulasi Prasad

2013-01-01

The accurate measurements on density of the binary mixtures of cetyltrimethylammonium bromide and sodium dodecyl sulphate in pure water and in methanol(1) + water (2) mixed solvent media containing (0.10, 0.20, and 0.30) volume fractions of methanol at 308.15, 318.15, and 323.15 K are reported. The concentrations are varied from (0.03 to 0.12) mol.l(-1) of sodium dodecyl sulphate in presence of ~ 5.0×10(-4) mol.l(-1) cetyltrimethylammonium bromide. The results showed almost increase in the densities with increasing surfactant mixture concentration, also the densities are found to decrease with increasing temperature over the entire concentration range, investigated in a given mixed solvent medium and these values are found to decrease with increasing methanol content in the solvent composition. The concentration dependence of the apparent molar volumes appear to be negligible over the entire concentration range, investigated in a given mixed solvent medium and the apparent molar volumes increase with increasing temperature and are found to decrease with increasing methanol content in the solvent composition.

Fast automated dual-syringe based dispersive liquid-liquid microextraction coupled with gas chromatography-mass spectrometry for the determination of polycyclic aromatic hydrocarbons in environmental water samples.

PubMed

Guo, Liang; Tan, Shufang; Li, Xiao; Lee, Hian Kee

2016-03-18

An automated procedure, combining low density solvent based solvent demulsification dispersive liquid-liquid microextraction (DLLME) with gas chromatography-mass spectrometry analysis, was developed for the determination of polycyclic aromatic hydrocarbons (PAHs) in environmental water samples. Capitalizing on a two-rail commercial autosampler, fast solvent transfer using a large volume syringe dedicated to the DLLME process, and convenient extract collection using a small volume microsyringe for better GC performance were enabled. Extraction parameters including the type and volume of extraction solvent, the type and volume of dispersive solvent and demulsification solvent, extraction and demulsification time, and the speed of solvent injection were investigated and optimized. Under the optimized conditions, the linearity ranged from 0.1 to 50 μg/L, 0.2 to 50 μg/L, and 0.5 to 50 μg/L, depending on the analytes. Limits of detection were determined to be between 0.023 and 0.058 μg/L. The method was applied to determine PAHs in environmental water samples. Copyright © 2016 Elsevier B.V. All rights reserved.

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

DOEpatents

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

1998-03-24

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

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

DOEpatents

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

1998-01-01

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

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

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

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

1990-03-08

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

SOLVENT EXTRACTION PROCESS

DOEpatents

Jonke, A.A.

1957-10-01

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

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

NASA Astrophysics Data System (ADS)

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

2016-12-01

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

Unraveling Entropic Rate Acceleration Induced by Solvent Dynamics in Membrane Enzymes.

PubMed

Kürten, Charlotte; Syrén, Per-Olof

2016-01-16

Enzyme catalysis evolved in an aqueous environment. The influence of solvent dynamics on catalysis is, however, currently poorly understood and usually neglected. The study of water dynamics in enzymes and the associated thermodynamical consequences is highly complex and has involved computer simulations, nuclear magnetic resonance (NMR) experiments, and calorimetry. Water tunnels that connect the active site with the surrounding solvent are key to solvent displacement and dynamics. The protocol herein allows for the engineering of these motifs for water transport, which affects specificity, activity and thermodynamics. By providing a biophysical framework founded on theory and experiments, the method presented herein can be used by researchers without previous expertise in computer modeling or biophysical chemistry. The method will advance our understanding of enzyme catalysis on the molecular level by measuring the enthalpic and entropic changes associated with catalysis by enzyme variants with obstructed water tunnels. The protocol can be used for the study of membrane-bound enzymes and other complex systems. This will enhance our understanding of the importance of solvent reorganization in catalysis as well as provide new catalytic strategies in protein design and engineering.

Solvent extraction: the coordination chemistry behind extractive metallurgy.

PubMed

Wilson, A Matthew; Bailey, Phillip J; Tasker, Peter A; Turkington, Jennifer R; Grant, Richard A; Love, Jason B

2014-01-07

The modes of action of the commercial solvent extractants used in extractive hydrometallurgy are classified according to whether the recovery process involves the transport of metal cations, M(n+), metalate anions, MXx(n-), or metal salts, MXx into a water-immiscible solvent. Well-established principles of coordination chemistry provide an explanation for the remarkable strengths and selectivities shown by most of these extractants. Reagents which achieve high selectivity when transporting metal cations or metal salts into a water-immiscible solvent usually operate in the inner coordination sphere of the metal and provide donor atom types or dispositions which favour the formation of particularly stable neutral complexes that have high solubility in the hydrocarbons commonly used in recovery processes. In the extraction of metalates, the structures of the neutral assemblies formed in the water-immiscible phase are usually not well defined and the cationic reagents can be assumed to operate in the outer coordination spheres. The formation of secondary bonds in the outer sphere using, for example, electrostatic or H-bonding interactions are favoured by the low polarity of the water-immiscible solvents.

Photonic Crystal Based Sensor for Organic Solvents and for Solvent-Water Mixtures

PubMed Central

Fenzl, Christoph; Hirsch, Thomas; Wolfbeis, Otto S.

2012-01-01

Monodisperse polystyrene nanoparticles with a diameter of 173 nm were incorporated into a polydimethylsiloxane matrix where they display an iridescent color that can be attributed to the photonic crystal effect. The film is of violet color if placed in plain water, but turns to red in the presence of the non-polar solvent n-hexane. Several solvents were studied in some detail. We show that such films are capable of monitoring the water content of ethanol/water mixtures, where only 1% (v/v) of water leads to a shift of the peak wavelength of reflected light by 5 nm. The method also can be applied to determine, both visually and instrumentally, the fraction of methanol in ethanol/methanol mixtures. Here, a fraction of 1% of methanol (v/v) results in a wavelength shift of 2 nm. The reflected wavelength is not influenced by temperature changes nor impeded by photobleaching. The signal changes are fully reversible and response times are <1 s. PMID:23235441

Stability and activity of lysozyme in stoichiometric and non-stoichiometric protic ionic liquid (PIL)-water systems

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.

Membrane augmented distillation to separate solvents from water

DOEpatents

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

2012-09-11

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

Method for removing hydrocarbon contaminants from solid materials

DOEpatents

Bala, Gregory A.; Thomas, Charles P.

1995-01-01

A system for removing hydrocarbons from solid materials. Contaminated solids are combined with a solvent (preferably terpene based) to produce a mixture. The mixture is washed with water to generate a purified solid product (which is removed from the system) and a drainage product. The drainage product is separated into a first fraction (consisting mostly of contaminated solvent) and a second fraction (containing solids and water). The first fraction is separated into a third fraction (consisting mostly of contaminated solvent) and a fourth fraction (containing residual solids and water). The fourth fraction is combined with the second fraction to produce a sludge which is separated into a fifth fraction (containing water which is ultimately reused) and a sixth fraction (containing solids). The third fraction is then separated into a seventh fraction (consisting of recovered solvent which is ultimately reused) and an eighth fraction (containing hydrocarbon waste).

Method for removing hydrocarbon contaminants from solid materials

DOEpatents

Bala, G.A.; Thomas, C.P.

1995-10-03

A system is described for removing hydrocarbons from solid materials. Contaminated solids are combined with a solvent (preferably terpene based) to produce a mixture. The mixture is washed with water to generate a purified solid product (which is removed from the system) and a drainage product. The drainage product is separated into a first fraction (consisting mostly of contaminated solvent) and a second fraction (containing solids and water). The first fraction is separated into a third fraction (consisting mostly of contaminated solvent) and a fourth fraction (containing residual solids and water). The fourth fraction is combined with the second fraction to produce a sludge which is separated into a fifth fraction (containing water which is ultimately reused) and a sixth fraction (containing solids). The third fraction is then separated into a seventh fraction (consisting of recovered solvent which is ultimately reused) and an eighth fraction (containing hydrocarbon waste). 4 figs.

Apparatus for removing hydrocarbon contaminants from solid materials

DOEpatents

Bala, G.A.; Thomas, C.P.

1996-02-13

A system is described for removing hydrocarbons from solid materials. Contaminated solids are combined with a solvent (preferably terpene based) to produce a mixture. The mixture is washed with water to generate a purified solid product (which is removed from the system) and a drainage product. The drainage product is separated into a first fraction (consisting mostly of contaminated solvent) and a second fraction (containing solids and water). The first fraction is separated into a third fraction (consisting mostly of contaminated solvent) and a fourth fraction (containing residual solids and water). The fourth fraction is combined with the second fraction to produce a sludge which is separated into a fifth fraction (containing water which is ultimately reused) and a sixth fraction (containing solids). The third fraction is then separated into a seventh fraction (consisting of recovered solvent which is ultimately reused) and an eighth fraction (containing hydrocarbon waste). 4 figs.

Apparatus for removing hydrocarbon contaminants from solid materials

DOEpatents

Bala, Gregory A.; Thomas, Charles P.

1996-01-01

A system for removing hydrocarbons from solid materials. Contaminated solids are combined with a solvent (preferably terpene based) to produce a mixture. The mixture is washed with water to generate a purified solid product (which is removed from the system) and a drainage product. The drainage product is separated into a first fraction (consisting mostly of contaminated solvent) and a second fraction (containing solids and water). The first fraction is separated into a third fraction (consisting mostly of contaminated solvent) and a fourth fraction (containing residual solids and water). The fourth fraction is combined with the second fraction to produce a sludge which is separated into a fifth fraction (containing water which is ultimately reused) and a sixth fraction (containing solids). The third fraction is then separated into a seventh fraction (consisting of recovered solvent which is ultimately reused) and an eighth fraction (containing hydrocarbon waste).

COMBINED EFFECTS OF SOLVENTS ON THE RAT'S AUDITORY SYSTEM: STYRENE AND TRICHLOROETHYLENE

EPA Science Inventory

Because exposures to toxic agents typically involve more than one substance, it is necessary to know if combined exposures pose different risks than those to single agents. any solvents have been implicated in central nervous disorders and some of them are known to produce hearin...

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

DOEpatents

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

2006-07-11

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

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

DOEpatents

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

2002-01-01

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

Lipophilic stinging nettle extracts possess potent anti-inflammatory activity, are not cytotoxic and may be superior to traditional tinctures for treating inflammatory disorders

PubMed Central

Johnson, Tyler A.; Sohn, Johann; Inman, Wayne D.; Bjeldanes, Leonard F.; Rayburn, Keith

2012-01-01

Extracts of four plant portions (roots, stems, leaves and flowers) of Urtica dioica, (the stinging nettle) were prepared using accelerated solvent extraction (ASE) involving water, hexanes, methanol and dichloromethane. The extracts were evaluated for their anti-inflammatory and cytotoxic activity in an NF-κB luciferase and MTT assay using macrophage immune (RAW264.7) cells. A standardized commercial ethanol extract of nettle leaves were also evaluated. The methanolic extract of the flowering portions displayed significant anti-inflammatory activity on par with the standard anti-inflammatory agent celastrol (1) but was moderately cytotoxic. Alternatively, the polar extracts (water, methanol, ethanol) of the roots, stems and leaves plant portions displayed moderate to weak anti-inflammatory activity, while the methanol and especially the water soluble extracts exhibited noticeable cytotoxicity. In contrast, the lipophilic dichloromethane extracts of the roots, stems and leaves exhibited potent anti-inflammatory effects ≥ 1 with minimal cytotoxicity to RAW264.7 cells. Collectively these results suggest that using lipophilic extracts of the roots, stems or leaves of stinging nettle may be more effective then traditional tinctures (water, methanol, ethanol) to undergo clinical evaluations for the treatment of inflammatory disorders including arthritis. A chemical investigation into the lipophillic extracts of stinging nettle to identify the bioactive compound(s) responsible for their observed anti-inflammatory activity is further warranted. PMID:23092723

Lipophilic stinging nettle extracts possess potent anti-inflammatory activity, are not cytotoxic and may be superior to traditional tinctures for treating inflammatory disorders.

PubMed

Johnson, Tyler A; Sohn, Johann; Inman, Wayne D; Bjeldanes, Leonard F; Rayburn, Keith

2013-01-15

Extracts of four plant portions (roots, stems, leaves and flowers) of Urtica dioica (the stinging nettle) were prepared using accelerated solvent extraction (ASE) involving water, hexanes, methanol and dichloromethane. The extracts were evaluated for their anti-inflammatory and cytotoxic activities in an NF-κB luciferase and MTT assay using macrophage immune (RAW264.7) cells. A standardized commercial ethanol extract of nettle leaves was also evaluated. The methanolic extract of the flowering portions displayed significant anti-inflammatory activity on par with a standard compound celastrol (1) but were moderately cytotoxic. Alternatively, the polar extracts (water, methanol, ethanol) of the roots, stems and leaves displayed moderate to weak anti-inflammatory activity, while the methanol and especially the water soluble extracts exhibited noticeable cytotoxicity. In contrast, the lipophilic dichloromethane extracts of the roots, stems and leaves exhibited potent anti-inflammatory effects greater than or equal to 1 with minimal cytotoxicity to RAW264.7 cells. Collectively these results suggest that using lipophilic extracts of stinging nettle may be more effective than traditional tinctures (water, methanol, ethanol) in clinical evaluations for the treatment of inflammatory disorders especially arthritis. A chemical investigation into the lipophilic extracts of stinging nettle to identify the bioactive compound(s) responsible for their observed anti-inflammatory activity is further warranted. Published by Elsevier GmbH.

Two-stage coal liquefaction without gas-phase hydrogen

DOEpatents

Stephens, H.P.

1986-06-05

A process is provided for the production of a hydrogen-donor solvent useful in the liquefaction of coal, wherein the water-gas shift reaction is used to produce hydrogen while simultaneously hydrogenating a donor solvent. A process for the liquefaction of coal using said solvent is also provided. The process enables avoiding the use of a separate water-gas shift reactor as well as high pressure equipment for liquefaction. 3 tabs.

Effects of Acids, Bases, and Heteroatoms on Proximal Radial Distribution Functions for Proteins.

PubMed

Nguyen, Bao Linh; Pettitt, B Montgomery

2015-04-14

The proximal distribution of water around proteins is a convenient method of quantifying solvation. We consider the effect of charged and sulfur-containing amino acid side-chain atoms on the proximal radial distribution function (pRDF) of water molecules around proteins using side-chain analogs. The pRDF represents the relative probability of finding any solvent molecule at a distance from the closest or surface perpendicular protein atom. We consider the near-neighbor distribution. Previously, pRDFs were shown to be universal descriptors of the water molecules around C, N, and O atom types across hundreds of globular proteins. Using averaged pRDFs, a solvent density around any globular protein can be reconstructed with controllable relative error. Solvent reconstruction using the additional information from charged amino acid side-chain atom types from both small models and protein averages reveals the effects of surface charge distribution on solvent density and improves the reconstruction errors relative to simulation. Solvent density reconstructions from the small-molecule models are as effective and less computationally demanding than reconstructions from full macromolecular models in reproducing preferred hydration sites and solvent density fluctuations.

Application of precipitation methods for the production of water-insoluble drug nanocrystals: production techniques and stability of nanocrystals.

PubMed

Xia, Dengning; Gan, Yong; Cui, Fude

2014-01-01

This review focuses on using precipitation (bottom-up) method to produce water-insoluble drug nanocrystals, and the stability issues of nanocrystals. The precipitation techniques for production of ultra-fine particles have been widely researched for last few decades. In these techniques, precipitation of solute is achieved by addition of a non-solvent for solute called anti-solvent to decrease the solvent power for the solute dissolved in a solution. The anti-solvent can be water, organic solvents or supercritical fluids. In this paper, efforts have been made to review the precipitation techniques involving the anti-solvent precipitation by simple mixing, impinging jet mixing, multi-inlet vortex mixing, the using of high-gravity, ultrasonic waves and supercritical fluids. The key to the success of yielding stable nanocrystals in these techniques is to control the nucleation kinetics and particle growth through mixing during precipitation based on crystallization theories. The stability issues of the nanocrystals, such as sedimentation, Ostwald ripening, agglomeration and cementing of crystals, change of crystalline state, and the approaches to stabilizing nanocrystals are also discussed in detail.

A Novel Mechanism for Chemical Sensing Based on Solvent-Fluorophore-Substrate Interaction: Highly Selective Alcohol and Water Sensor with Large Fluorescence Signal Contrast.

PubMed

Chung, Kyeongwoon; Yang, Da Seul; Jung, Jaehun; Seo, Deokwon; Kwon, Min Sang; Kim, Jinsang

2016-10-06

Differentiation of solvents having similar physicochemical properties, such as ethanol and methanol, is an important issue of interest. However, without performing chemical analyses, discrimination between methanol and ethanol is highly challenging due to their similarity in chemical structure as well as properties. Here, we present a novel type of alcohol and water sensor based on the subtle differences in interaction among solvent analytes, fluorescent organic molecules, and a mesoporous silica gel substrate. A gradual change in the chemical structure of the fluorescent diketopyrrolopyrrole (DPP) derivatives alters their interaction with the substrate and solvent analyte, which creates a distinct intermolecular aggregation of the DPP derivatives on the silica gel substrate depending on the solvent environment and produces a change in the fluorescence color and intensity as a sensory signal. The devised sensor device, which is fabricated with simple drop-casting of the DPP derivative solutions onto a silica gel substrate, exhibited a completely reversible fluorescence signal change with large fluorescence signal contrast, which allows selective solvent detection by simple optical observation with the naked eye under UV light. Superior selectivity of the alcohol and water sensor system, which can clearly distinguish among ethanol, methanol, ethylene glycol, and water, is demonstrated.

Microcalorimetric study of thermal unfolding of lysozyme in water/glycerol mixtures: An analysis by solvent exchange model

NASA Astrophysics Data System (ADS)

Spinozzi, Francesco; Ortore, Maria Grazia; Sinibaldi, Raffaele; Mariani, Paolo; Esposito, Alessandro; Cinelli, Stefania; Onori, Giuseppe

2008-07-01

Folded protein stabilization or destabilization induced by cosolvent in mixed aqueous solutions has been studied by differential scanning microcalorimetry and related to difference in preferential solvation of native and denatured states. In particular, the thermal denaturation of a model system formed by lysozyme dissolved in water in the presence of the stabilizing cosolvent glycerol has been considered. Transition temperatures and enthalpies, heat capacity, and standard free energy changes have been determined when applying a two-state denaturation model to microcalorimetric data. Thermodynamic parameters show an unexpected, not linear, trend as a function of solvent composition; in particular, the lysozyme thermodynamic stability shows a maximum centered at water molar fraction of about 0.6. Using a thermodynamic hydration model based on the exchange equilibrium between glycerol and water molecules from the protein solvation layer to the bulk, the contribution of protein-solvent interactions to the unfolding free energy and the changes of this contribution with solvent composition have been derived. The preferential solvation data indicate that lysozyme unfolding involves an increase in the solvation surface, with a small reduction of the protein-preferential hydration. Moreover, the derived changes in the excess solvation numbers at denaturation show that only few solvent molecules are responsible for the variation of lysozyme stability in relation to the solvent composition.

Porous structures of polymer films prepared by spin coating with mixed solvents under humid condition.

PubMed

Park, Min Soo; Joo, Wonchul; Kim, Jin Kon

2006-05-09

We investigate the effects of interfacial energy between water and solvent as well as polymer concentration on the formation of porous structures of polymer films prepared by spin coating of cellulose acetate butyrate (CAB) in mixed solvent of tetrahydrofuran (THF) and chloroform under humid condition. The interfacial energy between water and the solvent was gradually changed by the addition of chloroform to the solvent. At a high polymer concentration (0.15 g/cm3 in THF), porous structures were limited only at the top surfaces of CAB films, regardless of interfacial energies, due to the high viscosity of the solution. At a medium concentration (approximately 0.08 g/cm3 in THF), CAB film had relatively uniform pores at the top surface and very small pores inside the film because of the mixing of the water droplets with THF solution. When chloroform was added to THF, pores at the inner CAB film had a comparable size with those at the top surface because of the reduced degree of the mixing between the water droplets and the mixed solvent. A further decrease in polymer concentration (0.05 g/cm3 in THF) caused the final films to have a two-layer porous structure, and the size of pores at each layer was almost the same.

Cavities in molecular liquids and the theory of hydrophobic solubilities

NASA Technical Reports Server (NTRS)

Pohorille, A.; Pratt, L. R.; MacElroy, R. (Principal Investigator)

1990-01-01

Thermal configurational data on neat liquids are used to obtain the work of formation of hard spherical cavities of atomic size in six molecular solvents: n-hexane, n-dodecane, n-undecyl alcohol, chloroform, carbon tetrachloride, and water. These results are used to test a recent suggestion that the differences between nonaqueous solvents and liquid water in solvation of inert gases are not principally due to the hydrogen-bonded structure of liquid water but rather to the comparatively small size of the water molecule. The frequencies of occurrence of cavities in liquid water can be meaningfully distinguished from those in the organic solvents. Liquid water has a larger fractional free volume, but that free volume is distributed in smaller packets. With respect to cavity work, water is compared to a solvent of the same molecular density and composed of hard spheres of the same size as the water molecule. That comparison indicates that the hard-sphere liquid finds more ways to configure its free volume in order to accommodate an atomic solute of substantial size and thus, would be more favorable solvent for inert gases. The scaled particle model of inert gas solubility in liquid water predicts cavity works 20% below the numerical data for TIP4P water at 300 K and 1.0 g/cm3 for cavity radii near 2.0 angstroms. It is argued that the sign of this difference is just the sign that ought to be expected and that the magnitude of this difference measures structural differences between water and the directly comparable hard-sphere liquid. In conjunction with previous data, these results indicate that atomic sized cavities should be considered submacroscopic.

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

NASA Astrophysics Data System (ADS)

Yonetani, Yoshiteru

2017-12-01

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

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)

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

PubMed

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

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

Effect of Different Solvents on the Measurement of Phenolics and the Antioxidant Activity of Mulberry (Morus atropurpurea Roxb.) with Accelerated Solvent Extraction.

PubMed

Yang, Jiufang; Ou, XiaoQun; Zhang, Xiaoxu; Zhou, ZiYing; Ma, LiYan

2017-03-01

The effects of 9 different solvents on the measurement of the total phenolics and antioxidant activities of mulberry fruits were studied using accelerated solvent extraction (ASE). Sixteen to 22 types of phenolics (flavonols, flavan-3-ols, flavanol, hydroxycinnamic acids, hydroxybenzoic acids, and stilbenes) from different mulberry extracts were characterized and quantified using HPLC-MS/MS. The principal component analysis (PCA) was used to determine the suitable solvents to distinguish between different classes of phenolics. Additionally, the phenolic extraction abilities of ASE and ultrasound-assisted extraction (UAE) were compared. The highest extraction efficiency could be achieved by using 50% acidified methanol (50MA) as ASE solvents with 15.14 mg/gallic acid equivalents g dry weight of mulberry fruit. The PCA results revealed that the 50MA followed by 50% acidified acetone (50AA) was the most efficient solvent for the extraction of phenolics, particularly flavonols (627.12 and 510.31 μg/g dry weight, respectively), while water (W) was not beneficial to the extraction of all categories of phenolics. Besides, the results of 3 antioxidant capability assays (DPPH, ABTS free radical-scavenging assay, and ferric-reducing antioxidant power assay) showed that water-based organic solvents increased the antioxidant capabilities of the extracts compared with water or pure organic solvents. ASE was more suitable for the extraction of phenolics than UAE. © 2017 Institute of Food Technologists®.

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.

Solvent-dependent gating motions of an extremophilic lipase from Pseudomonas aeruginosa

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

Johnson, Quentin R.; Nellas, Ricky B.; Shen, Tongye

2012-07-25

Understanding how organic solvent-stable proteins can function in anhydrous and often complex solutions is essential for the study of the interaction of protein and molecular immiscible interfaces and the design of efficient industrial enzymes in nonaqueous solvents. Using an extremophilic lipase from Pseudomonas aeruginosa as an example, we investigated the conformational dynamics of an organic solvent-tolerant enzyme in complex solvent milieux. Four 100-ns molecular dynamics simulations of the lipase were performed in solvent systems: water, hexane, and two mixtures of hexane and water, 5% and 95% (w/w) hexane. Our results show a solvent-dependent structural change of the protein, especially inmore » the region that regulates the admission of the substrate. We observed that the lipase is much less flexible in hexane than in aqueous solution or at the immiscible interface. Quantified by the size of the accessible channel, the lipase in water has a closed-gate conformation and no access to the active site, while in the hexane-containing systems, the lipase is at various degrees of open-gate state, with the immiscible interface setup being in the widely open conformation ensembles. Furthermore, the composition of explicit solvents in the access channel showed a significant influence on the conformational dynamics of the protein. Interestingly, the slowest step (bottleneck) of the hexane-induced conformational switch seems to be correlated with the slow dehydration dynamics of the channel.« less

Interfacial free energy governs single polystyrene chain collapse in water and aqueous solutions.

PubMed

Li, Isaac T S; Walker, Gilbert C

2010-05-12

The hydrophobic interaction is significantly responsible for driving protein folding and self-assembly. To understand it, the thermodynamics, the role of water structure, the dewetting process surrounding hydrophobes, and related aspects have undergone extensive investigations. Here, we examine the hypothesis that polymer-solvent interfacial free energy is adequate to describe the energetics of the collapse of a hydrophobic homopolymer chain at fixed temperature, which serves as a much simplified model for studying the hydrophobic collapse of a protein. This implies that changes in polymer-solvent interfacial free energy should be directly proportional to the force to extend a collapsed polymer into a bad solvent. To test this hypothesis, we undertook single-molecule force spectroscopy on a collapsed, single, polystyrene chain in water-ethanol and water-salt mixtures where we measured the monomer solvation free energy from an ensemble average conformations. Different proportions within the binary mixture were used to create solvents with different interfacial free energies with polystyrene. In these mixed solvents, we observed a linear correlation between the interfacial free energy and the force required to extend the chain into solution, which is a direct measure of the solvation free energy per monomer on a single chain at room temperature. A simple analytical model compares favorably with the experimental results. This knowledge supports a common assumption that explicit water solvent may not be necessary for cases whose primary concerns are hydrophobic interactions and hydrophobic hydration.

Preparation of ultrafine grained copper nanoparticles via immersion deposit method

NASA Astrophysics Data System (ADS)

Abbasi-Kesbi, Fatemeh; Rashidi, Ali Mohammad; Astinchap, Bandar

2018-03-01

Today, the exploration about synthesis of nanoparticles is much of interest to materials scientists. In this work, copper nanoparticles have been successfully synthesized by immersion deposit method in the absence of any stabilizing and reducing agents. Copper (II) sulfate pentahydrate as precursor salt and distilled water and Ethylene glycol as solvents were used. The copper nanoparticles were deposited on plates of low carbon steel. The effects of copper sulfate concentrations and solvent type were investigated. X-ray diffraction, scanning electron microscopy and UV-Visible spectroscopy were taken to investigate the crystallite size, crystal structure, and morphology and size distribution and the growth process of the nanoparticles of obtained Cu particles. The results indicated that the immersion deposit method is a particularly suitable method for synthesis of semispherical copper nanoparticles with the crystallites size in the range of 22 to 37 nm. By increasing the molar concentration of copper sulfate in distilled water solvent from 0.04 to 0.2 M, the average particles size is increased from 57 to 81 nm. The better size distribution of Cu nanoparticles was achieved using a lower concentration of copper sulfate. By increasing the molar concentration of copper sulfate in water solvent from 0.04 to 0.2, the location of the SPR peak has shifted from 600 to 630 nm. The finer Cu nanoparticles were formed using ethylene glycol instead water as a solvent. Also, the agglomeration and overlapping of nanoparticles in ethylene glycol were less than that of water solvent.

Sequence- and Temperature-Dependent Properties of Unfolded and Disordered Proteins from Atomistic Simulations.

PubMed

Zerze, Gül H; Best, Robert B; Mittal, Jeetain

2015-11-19

We use all-atom molecular simulation with explicit solvent to study the properties of selected intrinsically disordered proteins and unfolded states of foldable proteins, which include chain dimensions and shape, secondary structure propensity, solvent accessible surface area, and contact formation. We find that the qualitative scaling behavior of the chains matches expectations from theory under ambient conditions. In particular, unfolded globular proteins tend to be more collapsed under the same conditions than charged disordered sequences of the same length. However, inclusion of explicit solvent in addition naturally captures temperature-dependent solvation effects, which results in an initial collapse of the chains as temperature is increased, in qualitative agreement with experiment. There is a universal origin to the collapse, revealed in the change of hydration of individual residues as a function of temperature: namely, that the initial collapse is driven by unfavorable solvation free energy of individual residues, which in turn has a strong temperature dependence. We also observe that in unfolded globular proteins, increased temperature also initially favors formation of native-like (rather than non-native-like) structure. Our results help to establish how sequence encodes the degree of intrinsic disorder or order as well as its response to changes in environmental conditions.

Efficient sample preparation method based on solvent-assisted dispersive solid-phase extraction for the trace detection of butachlor in urine and waste water samples.

PubMed

Aladaghlo, Zolfaghar; Fakhari, Alireza; Behbahani, Mohammad

2016-10-01

In this work, an efficient sample preparation method termed solvent-assisted dispersive solid-phase extraction was applied. The used sample preparation method was based on the dispersion of the sorbent (benzophenone) into the aqueous sample to maximize the interaction surface. In this approach, the dispersion of the sorbent at a very low milligram level was achieved by inserting a solution of the sorbent and disperser solvent into the aqueous sample. The cloudy solution created from the dispersion of the sorbent in the bulk aqueous sample. After pre-concentration of the butachlor, the cloudy solution was centrifuged and butachlor in the sediment phase dissolved in ethanol and determined by gas chromatography with flame ionization detection. Under the optimized conditions (solution pH = 7.0, sorbent: benzophenone, 2%, disperser solvent: ethanol, 500 μL, centrifuged at 4000 rpm for 3 min), the method detection limit for butachlor was 2, 3 and 3 μg/L for distilled water, waste water, and urine sample, respectively. Furthermore, the preconcentration factor was 198.8, 175.0, and 174.2 in distilled water, waste water, and urine sample, respectively. Solvent-assisted dispersive solid-phase extraction was successfully used for the trace monitoring of butachlor in urine and waste water samples. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Solvent Dependence of Lateral Charge Transfer in a Porphyrin Monolayer

DOE PAGES

Brennan, Bradley J.; Regan, Kevin P.; Durrell, Alec C.; ...

2016-12-19

Lateral charge transport in a redox)active monolayer can be utilized for solar energy harvesting. We chose the porphyrin system to study the influence of the solvent on lateral hole hopping, which plays a crucial role in the charge)transfer kinetics. We also examined the influence of water, acetonitrile, and propylene carbonate as solvents. Hole)hopping lifetimes varied by nearly three orders of magnitude among solvents, ranging from 3 ns in water to 2800 ns in propylene carbonate, and increased nonlinearly as a function of added acetonitrile in aqueous solvent mixtures. Our results elucidate the important roles of solvation, molecular packing dynamics, andmore » lateral charge)transfer mechanisms that have implications for all dye)sensitized photoelectrochemical device designs.« less

Synthesis of soluble conducting polymers by acoustic mixing

DOEpatents

Kane, Marie C.

2016-09-13

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

Nonaqueous electrocatalytic water oxidation by a surface-bound Ru(bda)(L)₂ complex.

PubMed

Sheridan, Matthew V; Sherman, Benjamin D; Wee, Kyung-Ryang; Marquard, Seth L; Gold, Alexander S; Meyer, Thomas J

2016-04-21

The rate of electrocatalytic water oxidation by the heterogeneous water oxidation catalyst [Ru(bda)(4-O(CH2)3P(O3H2)2-pyr)2], , (pyr = pyridine; bda = 2,2'-bipyridine-6,6'-dicarboxylate) on metal oxide surfaces is greatly enhanced relative to water as the solvent. In these experiments with propylene carbonate (PC) as the nonaqueous solvent, water is the limiting reagent. Mechanistic studies point to atom proton transfer (APT) as the rate limiting step in water oxidation catalysis.

The Interaction of Spacecraft Cabin Atmospheric Quality and Water Processing System Performance

NASA Technical Reports Server (NTRS)

Perry, Jay L.; Croomes, Scott D. (Technical Monitor)

2002-01-01

Although designed to remove organic contaminants from a variety of waste water streams, the planned U.S.- and present Russian-provided water processing systems onboard the International Space Station (ISS) have capacity limits for some of the more common volatile cleaning solvents used for housekeeping purposes. Using large quantities of volatile cleaning solvents during the ground processing and in-flight operational phases of a crewed spacecraft such as the ISS can lead to significant challenges to the water processing systems. To understand the challenges facing the management of water processing capacity, the relationship between cabin atmospheric quality and humidity condensate loading is presented. This relationship is developed as a tool to determine the cabin atmospheric loading that may compromise water processing system performance. A comparison of cabin atmospheric loading with volatile cleaning solvents from ISS, Mir, and Shuttle are presented to predict acceptable limits to maintain optimal water processing system performance.

Effects of pH changes in water-based solvents to isolate antibacterial activated extracts of natural products

NASA Astrophysics Data System (ADS)

Buang, Yohanes; Suwari, Ola, Antonius R. B.

2017-12-01

Effects of pH changes in solvents on isolation of antibacterial activities of natural product extracts were conducted in the present study. Sarang semut (M. pendens) tubers as the model material for the study was considered to be the strategic resource of natural products based on its biochemical and therapeutical effects. The water with pH 5, 7, 9, and 13 was used as the solvents. The antibacterial activities of the resulted extracts indicated that higher the working pH, higher activities of the resulted extracts. The extent activities of the resulted extracts followed the increasing pH of the maceration system. The study also found that higher pH of the working solvent, higher the amounts of the antibacterial extracts isolated from the sample matrix of the natural product. The higher pH of the water solvents plays essential roles to promote the antibacterial activities of the natural product extracts from M. pendens tubers.

What information can frictional properties of polymer brushes tell us?

NASA Astrophysics Data System (ADS)

Zhang, Zhenyu; Moxey, Mark; Morse, Andrew; Armes, Steven; Lewis, Andrew; Geoghegan, Mark; Leggett, Graham

2013-03-01

We have used friction force microscopy (FFM) to quantitatively examine surface grown zwitterionic polymer brushes: poly(2-(methacryloyloxy)ethyl phosphorylcholine) (PMPC), and to establish the correlation between its frictional behaviour to other intrinsic properties. In a good solvent, it was found that the coefficient of friction (μ) decreased with increasing film thickness. We conclude that the amount of bound solvent increases as the brush length increases, causing the osmotic pressure to increase and yielding a reduced tendency for the brush layer to deform under applied load. When measured in a series of alcohol/water mixtures, a significant increase in μ was observed for ethanol/water mixtures at a volume fraction of 90%. This is attributed to brush collapse due to co-nonsolvency, leading to loss of hydration of the brush chains and hence substantially reduced lubrication. We show that single asperity contact mechanics is strongly dependent on solvent quality. Friction-load relationship was found linear in methanol (good solvent), but sub-linear in water and ethanol (moderate solvent).

The effect of different anti-solvent and coconut shell content on properties of coconut shell regenerated cellulose biocomposite films

NASA Astrophysics Data System (ADS)

Hahary, Farah Norain; Husseinsyah, Salmah; Mostapha@Zakaria, Marliza

2016-07-01

In this study, coconut shell (CS) regenerated cellulose (RC) biocomposite films was prepared using dimethylacetamide/lithium chloride (DMAc/LiCl) solvent system. The effect of anti-solvents such as water and methanol for regeneration of cellulose and coconut shell content on properties of CS-RC biocomposite films was investigated. The used of water as anti-solvent for cellulose regeneration was found to have higher tensile properties compared to regenerated cellulose using methanol. Besides, the X-Ray diffraction (XRD) analysis also revealed that RC using water as anti-solvent have higher crystallinity index (CrI) than CS-RC biocomposite film using methanol. The tensile strength and modulus elasticity of CS-RC biocomposite films increased up to 3 wt% CS and decreased with further addition of CS. The elongation at break of CS-RC biocomposite films decreased with the increment of CS. The CrI of CS-RC bioocmposite films up to 3 wt% and decreased with at higher content of CS.

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.

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.

To Evaluate the Effect of Solvents and Different Relative Humidity Conditions on Thermal and Rheological Properties of Microcrystalline Cellulose 101 Using METHOCEL™ E15LV as a Binder.

PubMed

Jagia, Moksh; Trivedi, Maitri; Dave, Rutesh H

2016-08-01

The solvent used for preparing the binder solution in wet granulation can affect the granulation end point and also impact the thermal, rheological, and flow properties of the granules. The present study investigates the effect of solvents and percentage relative humidity (RH) on the granules of microcrystalline cellulose (MCC) with hydroxypropyl methyl cellulose (HPMC) as the binder. MCC was granulated using 2.5% w/w binder solution in water and ethanol/water mixture (80:20 v/v). Prepared granules were dried until constant percentage loss on drying, sieved, and further analyzed. Dried granules were exposed to different percentage RH for 48 h at room temperature. Powder rheometer was used for the rheological and flow characterization, while thermal effusivity and differential scanning calorimeter were used for thermal analysis. The thermal effusivity values for the wet granules showed a sharp increase beginning 50% w/w binder solution in both cases, which reflected the over-wetting of granules. Ethanol/water solvent batches showed greater resistance to flow as compared to the water solvent batches in the wet granule stage, while the reverse was true for the dried granule stage, as evident from the basic flowability energy values. Although the solvents used affected the equilibration kinetics of moisture content, the RH-exposed granules remained unaffected in their flow properties in both cases. This study indicates that the solvents play a vital role on the rheology and flow properties of MCC granules, while the different RH conditions have little or no effect on them for the above combination of solvent and binder.

Computational solvation dynamics of oxyquinolinium betaine linked to trehalose.

PubMed

Heid, Esther; Schröder, Christian

2016-10-28

Studying the changed water dynamics in the hydration layers of biomolecules is an important step towards fuller understanding of their function and mechanisms, but has shown to be quite difficult. The measurement of the time-dependent Stokes shift of a chromophore attached to the biomolecule is a promising method to achieve this goal, as published in Sajadi et al. [J. Phys. Chem. Lett., 5, 1845 (2014).] where trehalose was used as biomolecule, 1-methyl-6-oxyquinolinium betaine as chromophore, and water as solvent. An overall retardation of solvent molecules is then obtained by comparison of the linked system to the same system without trehalose, but contributions from different subgroups of solvent molecules, for example, molecules close to or far from trehalose, are unknown. The difficulty arising from these unknown contributions of retarded and possibly unretarded solvent molecules is overcome in this work by conducting computer simulations on this system and decomposing the overall signal into the contributions from various molecules at different locations. We performed non-equilibrium molecular dynamics simulation using a polarizable water model and a non-polarizable solute model and could reproduce the experimental time-dependent Stokes shift accurately for the linked trehalose-oxyquinolinium and the pure oxyquinolinium over a wide temperature range, indicating the correctness of our employed models. Decomposition of the shift into contributions from different solvent subgroups showed that the amplitude of the measured shift is made up only half by the desired retarded solvent molecules in the hydration layer, but to another half by unretarded bulk water, so that measured relaxation times of the overall Stokes shift are only a lower boundary for the true relaxation times in the hydration layer of trehalose. As a side effect, the results on the effect of trehalose on solvation dynamics contribute to the long standing debate on the range of influence of trehalose on water dynamics, the number of retarded solvent molecules, and the observed retardation factor when compared to bulk water.

Computational solvation dynamics of oxyquinolinium betaine linked to trehalose

NASA Astrophysics Data System (ADS)

Heid, Esther; Schröder, Christian

2016-10-01

Studying the changed water dynamics in the hydration layers of biomolecules is an important step towards fuller understanding of their function and mechanisms, but has shown to be quite difficult. The measurement of the time-dependent Stokes shift of a chromophore attached to the biomolecule is a promising method to achieve this goal, as published in Sajadi et al. [J. Phys. Chem. Lett., 5, 1845 (2014).] where trehalose was used as biomolecule, 1-methyl-6-oxyquinolinium betaine as chromophore, and water as solvent. An overall retardation of solvent molecules is then obtained by comparison of the linked system to the same system without trehalose, but contributions from different subgroups of solvent molecules, for example, molecules close to or far from trehalose, are unknown. The difficulty arising from these unknown contributions of retarded and possibly unretarded solvent molecules is overcome in this work by conducting computer simulations on this system and decomposing the overall signal into the contributions from various molecules at different locations. We performed non-equilibrium molecular dynamics simulation using a polarizable water model and a non-polarizable solute model and could reproduce the experimental time-dependent Stokes shift accurately for the linked trehalose-oxyquinolinium and the pure oxyquinolinium over a wide temperature range, indicating the correctness of our employed models. Decomposition of the shift into contributions from different solvent subgroups showed that the amplitude of the measured shift is made up only half by the desired retarded solvent molecules in the hydration layer, but to another half by unretarded bulk water, so that measured relaxation times of the overall Stokes shift are only a lower boundary for the true relaxation times in the hydration layer of trehalose. As a side effect, the results on the effect of trehalose on solvation dynamics contribute to the long standing debate on the range of influence of trehalose on water dynamics, the number of retarded solvent molecules, and the observed retardation factor when compared to bulk water.

Nanosized solvent superstructures in ultramolecular aqueous dilutions: twenty years' research using water proton NMR relaxation.

PubMed

Demangeat, Jean-Louis

2013-04-01

proton nuclear magnetic resonance (NMR) relaxation times T1, T2, T1/T2 are sensitive to motion and organization of water molecules. Especially, increase in T1/T2 reflects a higher degree of structuring. My purpose was to look at physical changes in water in ultrahigh aqueous dilutions. Samples were prepared by iterative centesimal (c) dilution with vigorous agitation, ranging between 3c and 24c (Avogadro limit 12c). Solutes were silica-lactose, histamine, manganese-lactose. Solvents were water, NaCl 0.15 M or LiCl 0.15 M. Solvents underwent strictly similar, simultaneous dilution/agitation, for each level of dilution, as controls. NMR relaxation was studied within 0.02-20 MHz. No changes were observed in controls. Increasing T1 and T1/T2 were found in dilutions, which persisted beyond 9c (manganese-lactose), 10c (histamine) and 12c (silica-lactose). For silica-lactose in LiCl, continuous decrease in T2 with increase in T1/T2 within the 12c-24c range indicated growing structuring of water despite absence of the initial solute. All changes vanished after heating/cooling. These findings were interpreted in terms of nanosized (>4-nm) supramolecular structures involving water, nanobubbles and ions, if any. Additional study of low dilutions of silica-lactose revealed increased T2 and decreased T1/T2 compared to solvent, within the 10(-3)-10(-6) range, reflecting transient solvent destructuring. This could explain findings at high dilution. Proton NMR relaxation demonstrated modifications of the solvent throughout the low to ultramolecular range of dilution. The findings suggested the existence of superstructures that originate stereospecifically around the solute after an initial destructuring of the solvent, developing more upon dilution and persisting beyond 12c. Copyright © 2013 The Faculty of Homeopathy. Published by Elsevier Ltd. All rights reserved.

40 CFR 60.624 - Test methods and procedures.

Code of Federal Regulations, 2010 CFR

2010-07-01

...-water separator. Near the end of the recovery cycle, the entire flow of recovered solvent should be... solvent from the solvent recovery dryer at the termination of the recovery cycle is no greater than 0.05... cycle and the monitoring procedure should continue until the flow rate of solvent is less than or equal...

40 CFR 60.624 - Test methods and procedures.

Code of Federal Regulations, 2014 CFR

2014-07-01

...-water separator. Near the end of the recovery cycle, the entire flow of recovered solvent should be... solvent from the solvent recovery dryer at the termination of the recovery cycle is no greater than 0.05... cycle and the monitoring procedure should continue until the flow rate of solvent is less than or equal...

40 CFR 60.624 - Test methods and procedures.

Code of Federal Regulations, 2013 CFR

2013-07-01

...-water separator. Near the end of the recovery cycle, the entire flow of recovered solvent should be... solvent from the solvent recovery dryer at the termination of the recovery cycle is no greater than 0.05... cycle and the monitoring procedure should continue until the flow rate of solvent is less than or equal...

40 CFR 60.624 - Test methods and procedures.

Code of Federal Regulations, 2012 CFR

2012-07-01

...-water separator. Near the end of the recovery cycle, the entire flow of recovered solvent should be... solvent from the solvent recovery dryer at the termination of the recovery cycle is no greater than 0.05... cycle and the monitoring procedure should continue until the flow rate of solvent is less than or equal...

Pressurized solvent extraction of pure food grade starch

USDA-ARS?s Scientific Manuscript database

A commercial pressurized solvent extractor was used to remove lipid and non-lipid material from cornstarch using n-propanol/water and ethanol/water mixtures. Yields and chemical composition of the extract fractions were determined. Cornstarch samples were characterized using pasting properties and...

[Effects of snow cover on water soluble and organic solvent soluble components during foliar litter decomposition in an alpine forest].

PubMed

Xu, Li-Ya; Yang, Wan-Qin; Li, Han; Ni, Xiang-Yin; He, Jie; Wu, Fu-Zhong

2014-11-01

Seasonal snow cover may change the characteristics of freezing, leaching and freeze-thaw cycles in the scenario of climate change, and then play important roles in the dynamics of water soluble and organic solvent soluble components during foliar litter decomposition in the alpine forest. Therefore, a field litterbag experiment was conducted in an alpine forest in western Sichuan, China. The foliar litterbags of typical tree species (birch, cypress, larch and fir) and shrub species (willow and azalea) were placed on the forest floor under different snow cover thickness (deep snow, medium snow, thin snow and no snow). The litterbags were sampled at snow formation stage, snow cover stage and snow melting stage in winter. The results showed that the content of water soluble components from six foliar litters decreased at snow formation stage and snow melting stage, but increased at snow cover stage as litter decomposition proceeded in the winter. Besides the content of organic solvent soluble components from azalea foliar litter increased at snow cover stage, the content of organic solvent soluble components from the other five foliar litters kept a continue decreasing tendency in the winter. Compared with the content of organic solvent soluble components, the content of water soluble components was affected more strongly by snow cover thickness, especially at snow formation stage and snow cover stage. Compared with the thicker snow covers, the thin snow cover promoted the decrease of water soluble component contents from willow and azalea foliar litter and restrain the decrease of water soluble component content from cypress foliar litter. Few changes in the content of water soluble components from birch, fir and larch foliar litter were observed under the different thicknesses of snow cover. The results suggested that the effects of snow cover on the contents of water soluble and organic solvent soluble components during litter decomposition would be controlled by litter quality.

Water dynamics in small reverse micelles in two solvents: two-dimensional infrared vibrational echoes with two-dimensional background subtraction.

PubMed

Fenn, Emily E; Wong, Daryl B; Fayer, M D

2011-02-07

Water dynamics as reflected by the spectral diffusion of the water hydroxyl stretch were measured in w(0) = 2 (1.7 nm diameter) Aerosol-OT (AOT)/water reverse micelles in carbon tetrachloride and in isooctane solvents using ultrafast 2D IR vibrational echo spectroscopy. Orientational relaxation and population relaxation are observed for w(0) = 2, 4, and 7.5 in both solvents using IR pump-probe measurements. It is found that the pump-probe observables are sensitive to w(0), but not to the solvent. However, initial analysis of the vibrational echo data from the water nanopool in the reverse micelles in the isooctane solvent seems to yield different dynamics than the CCl(4) system in spite of the fact that the spectra, vibrational lifetimes, and orientational relaxation are the same in the two systems. It is found that there are beat patterns in the interferograms with isooctane as the solvent. The beats are observed from a signal generated by the AOT/isooctane system even when there is no water in the system. A beat subtraction data processing procedure does a reasonable job of removing the distortions in the isooctane data, showing that the reverse micelle dynamics are the same within experimental error regardless of whether isooctane or carbon tetrachloride is used as the organic phase. Two time scales are observed in the vibrational echo data, ~1 and ~10 ps. The slower component contains a significant amount of the total inhomogeneous broadening. Physical arguments indicate that there is a much slower component of spectral diffusion that is too slow to observe within the experimental window, which is limited by the OD stretch vibrational lifetime.

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

DOE PAGES

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

2017-08-18

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

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

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

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

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

Water dynamics in small reverse micelles in two solvents: Two-dimensional infrared vibrational echoes with two-dimensional background subtraction

NASA Astrophysics Data System (ADS)

Fenn, Emily E.; Wong, Daryl B.; Fayer, M. D.

2011-02-01

Water dynamics as reflected by the spectral diffusion of the water hydroxyl stretch were measured in w0 = 2 (1.7 nm diameter) Aerosol-OT (AOT)/water reverse micelles in carbon tetrachloride and in isooctane solvents using ultrafast 2D IR vibrational echo spectroscopy. Orientational relaxation and population relaxation are observed for w0 = 2, 4, and 7.5 in both solvents using IR pump-probe measurements. It is found that the pump-probe observables are sensitive to w0, but not to the solvent. However, initial analysis of the vibrational echo data from the water nanopool in the reverse micelles in the isooctane solvent seems to yield different dynamics than the CCl4 system in spite of the fact that the spectra, vibrational lifetimes, and orientational relaxation are the same in the two systems. It is found that there are beat patterns in the interferograms with isooctane as the solvent. The beats are observed from a signal generated by the AOT/isooctane system even when there is no water in the system. A beat subtraction data processing procedure does a reasonable job of removing the distortions in the isooctane data, showing that the reverse micelle dynamics are the same within experimental error regardless of whether isooctane or carbon tetrachloride is used as the organic phase. Two time scales are observed in the vibrational echo data, ~1 and ~10 ps. The slower component contains a significant amount of the total inhomogeneous broadening. Physical arguments indicate that there is a much slower component of spectral diffusion that is too slow to observe within the experimental window, which is limited by the OD stretch vibrational lifetime.

TES buffer-induced phase separation of aqueous solutions of several water-miscible organic solvents at 298.15 K: phase diagrams and molecular dynamic simulations.

PubMed

Taha, Mohamed; Lee, Ming-Jer

2013-06-28

Water and the organic solvents tetrahydrofuran, 1,3-dioxolane, 1,4-dioxane, 1-propanol, 2-propanol, tert-butanol, acetonitrile, or acetone are completely miscible in all proportions at room temperature. Here, we present new buffering-out phase separation systems that the above mentioned organic aqueous solutions can be induced to form two liquid phases in the presence of a biological buffer 2-[[1,3-dihydroxy-2-(hydroxymethyl)propan-2-yl]amino]ethanesulfonic acid (TES). The lower liquid phase is rich in water and buffer, and the upper phase is organic rich. This observation has both practical and mechanistic interests. The phase diagrams of these systems were constructed by experimental measurements at ambient conditions. Molecular dynamic (MD) simulations were performed for TES + water + THF system to understand the interactions between TES, water, and organic solvent at molecular level. Several composition-sets for this system, beyond and inside the liquid-liquid phase-splitting region, have been simulated. Interestingly, the MD simulation for compositions inside the phase separation region showed that THF molecules are forced out from the water network to start forming a new liquid phase. The hydrogen-bonds, hydrogen-bonds lifetimes, hydrogen-bond energies, radial distribution functions, coordination numbers, the electrostatic interactions, and the van der Waals interactions between the different pairs have been calculated. Additionally, MD simulations for TES + water + tert-butanol∕acetonitrile∕acetone phase separation systems were simulated. The results from MD simulations provide an explanation for the buffering-out phenomena observed in [TES + water + organic solvent] systems by a mechanism controlled by the competitive interactions of the buffer and the organic solvent with water. The molecular mechanism reported here is helpful for designing new benign separation materials.

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

PubMed

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

2018-01-11

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

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

PubMed Central

2017-01-01

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

Solvent removal during synthetic and Nephila fiber spinning.

PubMed

Kojic, Nikola; Kojic, Milos; Gudlavalleti, Sauri; McKinley, Gareth

2004-01-01

The process by which spiders make their mechanically superior fiber involves removal of solvent (water) from a concentrated protein solution while the solution flows through a progressively narrowing spinning canal. Our aim was to determine a possible mechanism of spider water removal by using a computational model. To develop appropriate computational techniques for modeling of solvent removal during fiber spinning, a study was first performed using a synthetic solution. In particular, the effect of solvent removal during elongational flow (also exhibited in the spinning canal of the spider) on fiber mechanical properties was examined. The study establishes a model for solvent removal during dry spinning of synthetic fibers, assuming that internal diffusion governs solvent removal and that convective resistance is small. A variable internal solvent diffusion coefficient, dependent on solvent concentration, is also taken into account in the model. An experimental setup for dry (air) spinning was used to make fibers whose diameter was on the order of those made by spiders (approximately 1 microm). Two fibers of different thickness, corresponding to different spinning conditions, were numerically modeled for solvent removal and then mechanically tested. These tests showed that the thinner fiber, which lost more solvent under elongational flow, had 5-fold better mechanical properties (elastic modulus of 100 MPa and toughness of 15 MJ/m3) than the thicker fiber. Even though the mechanical properties were far from those of dragline spider silk (modulus of 10 GPa and toughness of 150 MJ/m3), the experimental methodology and numerical principles developed for the synthetic case proved to be valuable when establishing a model for the Nephila spinning process. In this model, an assumption of rapid convective water removal at the spinning canal wall was made, with internal diffusion of water through the fiber as the governing process. Then the diffusion coefficient of water through the initial spinning solution, obtained ex vivo from the Nephila clavipes major ampullate gland, was determined and incorporated into the numerical procedure, along with the wall boundary conditions and canal geometry. Also, a typical fiber reeling speed during web making, as well as the assumption of a dry exiting fiber, were included in the model. The results show that a cross-section of spinning solution (dope), which is initially 70% water, spends 19 s in the spinning canal in order to emerge dry. While the dope cross-section traverses the canal, its velocity increases from 0.37 mm/s at the entrance to 12.5 mm/s at the canal exit. The obtained results thus indicate that simple diffusion, along with the dry wall boundary condition, is a viable mechanism for water removal during typical Nephila fiber spinning.

The production of ultrathin polyimide films for the solar sail program and Large Space Structures Technology (LSST): A feasibility study

NASA Technical Reports Server (NTRS)

Forester, R. H.

1978-01-01

Polyimide membranes of a thickness range from under 0.01 micron m to greater than 1 micron m can be produced at an estimated cost of 50 cents per sq m (plus the cost of the polymer). The polymer of interest is dissolved in a solvent which is solube in water. The polymer or casting solution is allowed to flow down an inclined ramp onto a water surface where a pool of floating polymer develops. The solvent dissolves into the water lowering the surface tension of the water on equently, the contact angle of the polymer pool is very low and the edge of the pool is very thin. The solvent dissolves from this thin region too rapidly to be replenished from the bulk of the pool and a solid polymer film forms. Firm formation is rapid and spontaneous and the film spreads out unaided, many feet from the leading edge of the pool. The driving force for this process is the exothermic solution of the organic solvent from the polymer solution into the water.

Fluorescence sensor for water in organic solvents prepared from covalent immobilization of 4-morpholinyl-1, 8-naphthalimide.

PubMed

Niu, Cheng-Gang; Qin, Pin-Zhu; Zeng, Guang-Ming; Gui, Xiao-Qin; Guan, Ai-Ling

2007-02-01

A new fluorescent dye, N-allyl-4-morpholinyl-1,8-naphthalimide (AMN), was synthesized as a fluorescence indicator in the fabrication of a sensor for determining water content in organic solvents. To prevent leakage of the fluorophore, AMN was photo-copolymerized with acrylamide, (2-hydroxyethyl)methacrylate, and triethylene glycol dimethacrylate on a glass surface treated with a silanizing agent. The sensing mechanism is based on the solvatochromic feature of the covalently immobilized AMN. The fluorescence intensity of AMN decreased with increasing water contents when it was excited at 400 nm. In the range of ca. 0.00-4.40% (v/v), the fluorescence intensity of AMN changed as a linear function of water content. The sensor exhibited satisfactory reproducibility, reversibility, and a response time (t (99)) of the order of 50 s. The detection limit was solvent-dependent, when acetonitrile was used as the solvent, and the detection limit could be as low as 0.006% (v/v) of water. Additionally, the prepared sensor is pH-insensitive and possesses a relatively long lifetime of at least one month.

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

PubMed

Jinno, Naoya; Hashimoto, Masahiko; Tsukagoshi, Kazuhiko

2011-01-01

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

A hydro/organo/hybrid gelator: a peptide lipid with turning aspartame head groups.

PubMed

Mukai, Masaru; Minamikawa, Hiroyuki; Aoyagi, Masaru; Asakawa, Masumi; Shimizu, Toshimi; Kogiso, Masaki

2013-04-01

This work presents a novel bola-type peptide lipid which can gelate water, organic solvents, and water/organic-solvent mixtures. In its molecular structure, an amphiphilic dipeptide aspartame (L-α-aspartyl-L-phenylalanine methyl ester) is connected at both ends of an alkylene linker. The different morphologies in the hydrogel (helical nanotapes) and the organogel (tape-like nanostructures) were visualized by energy-filtering transmission electron microscopy (EF-TEM) and energy-filtering scanning electron microscopy (FE-SEM), and the molecular arrangement was examined using X-ray diffraction (XRD), infrared (IR) spectroscopy, and circular dichroism (CD) spectroscopy. Possessing a hydrophilic aspartic acid group and a (relatively) hydrophobic phenylalanine methyl ester group, the dipeptide head group can turn about in response to solvent polarity. As a consequence, the solvent condition changed the molecular packing of the gelator and affected the overall supramolecular structure of the gel. It is noted that the peptide lipid gelated mixed solvents of water and organic solvents such as dichloromethane, liquid-paraffin, olive-oil, silicone-oils, and so on. The present hybrid gel can simultaneously hold hydrophilic and hydrophobic functional materials. Copyright © 2013 Elsevier Inc. All rights reserved.

Effects of Acids, Bases, and Heteroatoms on Proximal Radial Distribution Functions for Proteins

PubMed Central

Nguyen, Bao Linh; Pettitt, B. Montgomery

2015-01-01

The proximal distribution of water around proteins is a convenient method of quantifying solvation. We consider the effect of charged and sulfur-containing amino acid side-chain atoms on the proximal radial distribution function (pRDF) of water molecules around proteins using side-chain analogs. The pRDF represents the relative probability of finding any solvent molecule at a distance from the closest or surface perpendicular protein atom. We consider the near-neighbor distribution. Previously, pRDFs were shown to be universal descriptors of the water molecules around C, N, and O atom types across hundreds of globular proteins. Using averaged pRDFs, a solvent density around any globular protein can be reconstructed with controllable relative error. Solvent reconstruction using the additional information from charged amino acid side-chain atom types from both small models and protein averages reveals the effects of surface charge distribution on solvent density and improves the reconstruction errors relative to simulation. Solvent density reconstructions from the small-molecule models are as effective and less computationally demanding than reconstructions from full macromolecular models in reproducing preferred hydration sites and solvent density fluctuations. PMID:26388706

NEPTUNIUM SOLVENT EXTRACTION PROCESS

DOEpatents

Dawson, L.R.; Fields, P.R.

1959-10-01

The separation of neptunium from an aqueous solution by solvent extraction and the extraction of neptunium from the solvent solution are described. Neptunium is separated from an aqueous solution containing tetravalent or hexavalent neptunium nitrate, nitric acid, and a nitrate salting out agent, such as sodium nitrate, by contacting the solution with an organic solvent such as diethyl ether. Subsequently, the neptunium nitrate is extracted from the organic solvent extract phase with water.

RELATIONSHIP BETWEEN DEHALOCOCCOIDES DNA IN GROUND WATER AND NATURAL ATTENUATION OF CHLORINATED SOLVENTS

EPA Science Inventory

Biological reductive dechlorination is the primary mechanism for natural attenuation of chlorinated solvents in ground water. The only organisms that are known to completely dechlorinate cis-DCE past vinyl chloride to ethylene or ethane are members of the Dehalococcoides group. ...

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.

COSOLVENCY AND SOPRTION OF HYDROPHOBIC ORGANIC CHEMICALS

EPA Science Inventory

Sorption of hydrophobic organic chemicals (HOCs) by two soils was measured from mixed solvents containing water plus completely miscible organic solvents (CMOSs) and partially miscible organic solvents (PMOSs). The utility of the log-linear cosolvency model for predicting HOC sor...

REMEDIATION OF CONTAMINATED SOILS BY SOLVENT FLUSHING

EPA Science Inventory

Solvent flushing is a potential technique for remediating a waste disposal/spill site contaminated with organic chemicals. This technique involves the injection of a solvent mixture (e.g., water plus alcohols) that enhances contaminant solubility, reduces the retardation factor, ...

Biofoam II

DOEpatents

Morrison, R.L.

1994-11-01

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

Biofoam II

DOEpatents

Morrison, Robert L.

1994-01-01

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

Solvent/co-solvent effects on the electronic properties and adsorption mechanism of anticancer drug Thioguanine on Graphene oxide surface as a nanocarrier: Density functional theory investigation and a molecular dynamics

NASA Astrophysics Data System (ADS)

Hasanzade, Zohre; Raissi, Heidar

2017-11-01

In this work, the adsorption of Thioguanine (TG) anticancer drug on the surface of Graphene oxide (GO) nanosheet has investigated using density functional theory (DFT) and molecular dynamics simulation (MDs). Quantum mechanics calculations by two methods including M06-2X/6-31G**and ωB97X-D/6-31G** have been employed to calculate the details of energetic, geometric, and electronic properties of the TG molecule interacting with Graphene oxide nanosheet (GONS). DFT calculations confirmed that the strongest adsorption is observed when hydrogen bond interactions between TG molecule and the functional groups of Graphene oxide nanosheet are predominate. In all calculations, solvent effects have been considered in water using the PCM method. It is found that TG molecule can be adsorbed on Graphene oxide with negative solvation energy, indicating the TG adsorption on Graphene oxide surfaces is thermodynamically favored. Moreover, MD simulations are examined to understand the solvent/co-solvent effect (water, ethanol, nicotine) on the Thioguanine drug delivery through Graphene oxide. The results of RDF patterns and the van der Waals energy calculations show that interaction between TG drugs and the Graphene oxide surface is stronger in water solvent compared to the other co-solvent. The obtained MD results illustrate that when nicotine and ethanol exist in the system, the drug takes longer time to bind with GO nanosheet and the system becomes unstable. It can be concluded that Graphene oxide can be a promising candidate in water media for delivery the TG molecule.

Potential of mean force between two hydrophobic solutes in water.

PubMed

Southall, Noel T; Dill, Ken A

2002-12-10

We study the potential of mean force between two nonpolar solutes in the Mercedes Benz model of water. Using NPT Monte Carlo simulations, we find that the solute size determines the relative preference of two solute molecules to come into contact ('contact minimum') or to be separated by a single layer of water ('solvent-separated minimum'). Larger solutes more strongly prefer the contacting state, while smaller solutes have more tendency to become solvent-separated, particularly in cold water. The thermal driving forces oscillate with solute separation. Contacts are stabilized by entropy, whereas solvent-separated solute pairing is stabilized by enthalpy. The free energy of interaction for small solutes is well-approximated by scaled-particle theory. Copyright 2002 Elsevier Science B.V.

Conversion from solvent rinsable fluxes to aqueous rinsable fluxes for hot oil solder leveling

NASA Astrophysics Data System (ADS)

1992-03-01

A water rinsable flux was evaluated for hot oil solder leveling of printed wiring boards. The previously used rosin-activated flux required a solvent containing a chlorinated hydrocarbon for removing the flux residues after soldering. The water rinsable flux requires hot water or a solution of hot detergent for removing flux residues after smoldering. The water rinsable flux produced an acceptable soldered surface. Flux residues were removed by either hot water (120 F) or a solution of hot detergent (120 F).

Dynamics of water in sulfonated poly(phenylene) membranes

NASA Astrophysics Data System (ADS)

Osti, Naresh; Etampawala, Thusitha; Shrestha, Umesh; Perahia, Dvora; Cornelius, Christopher

2011-03-01

The dynamics of water in networks formed by highly rigid ionic polymers, sulfonated poly(phenylene) as observed by quasi elastic neutron scattering (QENS) is presented. These rigid ionic polymers have potential as effective ion exchange membranes with impact on a large number of applications from water purification to clean energy, where its rigidity distinguishes it from other ionic polymers. Its transport characteristics are affected by its rigidness as well as by direct interactions with the solvent. Our QENS studies as a function of sulfonation levels, temperature and solvent content have shown that on the time scale of the measurement, the polymers are rigid. While macroscopically all samples swell, and transport water, the water molecules appear locally rather confined. Water however remind non-frozen to subzero temperatures. The results will be discussed in view of theoretical models including continues diffusion and hopping of solvent molecules.

Computational Elucidation of a Role That Brønsted Acidification of the Lewis Acid-Bound Water Might Play in the Hydrogenation of Carbonyl Compounds with H2 in Lewis Basic Solvents.

PubMed

Heshmat, Mojgan; Privalov, Timofei

2017-08-25

Brønsted acidification of water by Lewis acid (LA) complexation is one of the fundamental principles in chemistry. Using transition-state calculations (TS), herein we investigate the role that Brønsted acidification of the LA-bound water might play in the mechanism of the hydrogenation of carbonyl compounds in Lewis basic solvents under non-anhydrous conditions. The potential energy scans and TS calculations were carried out with a series of eight borane LAs as well as the commonly known strong LA AlCl 3 in 1,4-dioxane or THF as Lewis basic solvents. Our molecular model consists of the dative LA-water adduct with hydrogen bonds to acetone and a solvent molecule plus one additional solvent molecule that participates is the TS structure describing the cleavage of H 2 at acetone's carbonyl carbon atom. In all the molecular models applied here, acetone (O=CMe 2 ) is the archetypical carbonyl substrate. We demonstrate that Brønsted acidification of the LA-bound water can indeed lower the barrier height of the solvent-involving H 2 -cleavage at the acetone's carbonyl carbon atom. This is significant because at present it is believed that the mechanism of the herein considered reaction is described by the same mechanism regardless of whether the reaction conditions are strictly anhydrous or non-anhydrous. Our results offer an alternative to this belief that warrants consideration and further study. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Aspects of Solvent Chemistry for Calcium Hydroxide Medicaments

PubMed Central

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

Communication: Contrasting effects of glycerol and DMSO on lipid membrane surface hydration dynamics and forces

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

Schrader, Alex M.; Cheng, Chi-Yuan; Israelachvili, Jacob N.

2016-07-28

Glycerol and dimethyl sulfoxide (DMSO) are commonly used cryoprotectants in cellular systems, but due to the challenges of measuring the properties of surface-bound solvent, fundamental questions remain regarding the concentration, interactions, and conformation of these solutes at lipid membrane surfaces. We measured the surface water diffusivity at gel-phase dipalmitoylphosphatidylcholine (DPPC) bilayer surfaces in aqueous solutions containing ≤7.5 mol. % of DMSO or glycerol using Overhauser dynamic nuclear polarization. We found that glycerol similarly affects the diffusivity of water near the bilayer surface and that in the bulk solution (within 20%), while DMSO substantially increases the diffusivity of surface water relativemore » to bulk water. We compare these measurements of water dynamics with those of equilibrium forces between DPPC bilayers in the same solvent mixtures. DMSO greatly decreases the range and magnitude of the repulsive forces between the bilayers, whereas glycerol increases it. We propose that the differences in hydrogen bonding capability of the two solutes leads DMSO to dehydrate the lipid head groups, while glycerol affects surface hydration only as much as it affects the bulk water properties. The results suggest that the mechanism of the two most common cryoprotectants must be fundamentally different: in the case of DMSO by decoupling the solvent from the lipid surface, and in the case of glycerol by altering the hydrogen bond structure and intermolecular cohesion of the global solvent, as manifested by increased solvent viscosity.« less

Comparison of MICs of Fluconazole and Flucytosine When Dissolved in Dimethyl Sulfoxide or Water

PubMed Central

Fothergill, Annette W.; Sanders, Carmita

2013-01-01

A total of 145 clinical strains of Candida species were tested by the Clinical and Laboratory Standards Institute M27-A3 methodology to determine if replacing water with dimethyl sulfoxide as the solvent for fluconazole and flucytosine impacted the in vitro potency. No significant differences in MIC values were observed with either antifungal between the two solvents against any Candida species, and the essential agreement for each agent between the two solvents was greater than 99%. PMID:23576540

Estimating system parameters for solvent-water and plant cuticle-water using quantum chemically estimated Abraham solute parameters.

PubMed

Liang, Yuzhen; Torralba-Sanchez, Tifany L; Di Toro, Dominic M

2018-04-18

Polyparameter Linear Free Energy Relationships (pp-LFERs) using Abraham system parameters have many useful applications. However, developing the Abraham system parameters depends on the availability and quality of the Abraham solute parameters. Using Quantum Chemically estimated Abraham solute Parameters (QCAP) is shown to produce pp-LFERs that have lower root mean square errors (RMSEs) of predictions for solvent-water partition coefficients than parameters that are estimated using other presently available methods. pp-LFERs system parameters are estimated for solvent-water, plant cuticle-water systems, and for novel compounds using QCAP solute parameters and experimental partition coefficients. Refitting the system parameter improves the calculation accuracy and eliminates the bias. Refitted models for solvent-water partition coefficients using QCAP solute parameters give better results (RMSE = 0.278 to 0.506 log units for 24 systems) than those based on ABSOLV (0.326 to 0.618) and QSPR (0.294 to 0.700) solute parameters. For munition constituents and munition-like compounds not included in the calibration of the refitted model, QCAP solute parameters produce pp-LFER models with much lower RMSEs for solvent-water partition coefficients (RMSE = 0.734 and 0.664 for original and refitted model, respectively) than ABSOLV (4.46 and 5.98) and QSPR (2.838 and 2.723). Refitting plant cuticle-water pp-LFER including munition constituents using QCAP solute parameters also results in lower RMSE (RMSE = 0.386) than that using ABSOLV (0.778) and QSPR (0.512) solute parameters. Therefore, for fitting a model in situations for which experimental data exist and system parameters can be re-estimated, or for which system parameters do not exist and need to be developed, QCAP is the quantum chemical method of choice.

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

PubMed

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

2018-05-01

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

Experimental determination of solvent-water partition coefficients and Abraham parameters for munition constituents.

PubMed

Liang, Yuzhen; Kuo, Dave T F; Allen, Herbert E; Di Toro, Dominic M

2016-10-01

There is concern about the environmental fate and effects of munition constituents (MCs). Polyparameter linear free energy relationships (pp-LFERs) that employ Abraham solute parameters can aid in evaluating the risk of MCs to the environment. However, poor predictions using pp-LFERs and ABSOLV estimated Abraham solute parameters are found for some key physico-chemical properties. In this work, the Abraham solute parameters are determined using experimental partition coefficients in various solvent-water systems. The compounds investigated include hexahydro-1,3,5-trinitro-1,3,5-triazacyclohexane (RDX), octahydro-1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane (HMX), hexahydro-1-nitroso-3,5-dinitro-1,3,5-triazine (MNX), hexahydro-1,3,5-trinitroso-1,3,5-triazine (TNX), hexahydro-1,3-dinitroso-5- nitro-1,3,5-triazine (DNX), 2,4,6-trinitrotoluene (TNT), 1,3,5-trinitrobenzene (TNB), and 4-nitroanisole. The solvents in the solvent-water systems are hexane, dichloromethane, trichloromethane, octanol, and toluene. The only available reported solvent-water partition coefficients are for octanol-water for some of the investigated compounds and they are in good agreement with the experimental measurements from this study. Solvent-water partition coefficients fitted using experimentally derived solute parameters from this study have significantly smaller root mean square errors (RMSE = 0.38) than predictions using ABSOLV estimated solute parameters (RMSE = 3.56) for the investigated compounds. Additionally, the predictions for various physico-chemical properties using the experimentally derived solute parameters agree with available literature reported values with prediction errors within 0.79 log units except for water solubility of RDX and HMX with errors of 1.48 and 2.16 log units respectively. However, predictions using ABSOLV estimated solute parameters have larger prediction errors of up to 7.68 log units. This large discrepancy is probably due to the missing R2NNO2 and R2NNO2 functional groups in the ABSOLV fragment database. Copyright © 2016. Published by Elsevier Ltd.

What's new in the proton transfer reaction from pyranine to water? A femtosecond study of the proton transfer dynamics

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

Prayer, C.; Gustavsson, T.; Tran-Thi, T.-H.

1996-04-01

The proton transfer from excited pyranine to water is studied by the femtosecond fluorescence upconversion technique. It is shown for the first time that the proton transfer reaction in water proceeds by three successive steps: the solvent cage relaxation, the specific solute-solvent hydrogen-bond formation and finally the ion pair dissociation/diffusion.

Longitudinal relaxation properties of 1HN and 1Hα determined by direct-detected 13C NMR experiments to study intrinsically disordered proteins (IDPs)

NASA Astrophysics Data System (ADS)

Hošek, Tomáš; Gil-Caballero, Sergi; Pierattelli, Roberta; Brutscher, Bernhard; Felli, Isabella C.

2015-05-01

Intrinsically disordered proteins (IDPs) are functional proteins containing large fragments characterized by high local mobility. Bioinformatic studies have suggested that a significant fraction (more than 30%) of eukaryotic proteins has disordered regions of more than 50 amino acids in length. Hence, NMR methods for the characterization of local compactness and solvent accessibility in such highly disordered proteins are of high importance. Among the available approaches, the HET-SOFAST/BEST experiments (Schanda et al., 2006, Rennella et al., 2014) provide semi-quantitative information by monitoring longitudinal 1H relaxation of amide protons under different initial conditions. However, when approaching physiological sample conditions, the potential of these amide 1H detected experiments is reduced due to rapid amide proton solvent exchange. 13C direct detection methods therefore provide a valuable alternative thanks to a higher chemical shift dispersion and their intrinsic insensitivity toward solvent exchange. Here we present two sets of 13C-detected experiments, which indirectly measure 1HN and 1Hα inversion recovery profiles. The experiments consist of an initial spin inversion-recovery block optimized for selective manipulation of different types of proton spins followed by a CON read-out scheme. The proposed experiments were tested on human α-synuclein and ubiquitin, two representative examples of unfolded and folded proteins.

EFFECT OF SOLVENTS IN WATER ON ELECTROCATALYTIC DECHLORINATION OF 2-CL BP AT A PALLADIUM MODIFIED GRANULAR-GRAPHITE ELECTRODE

EPA Science Inventory

Remediation of soils and sediments contaminated by polychlorinated biphenyls (PCBs) usually involves use of organic solvents because PCBs have very limited solubility in water. The resulting liquids require further treatment to degrade these toxic contaminants. Catalytic and elec...

COMPARISON OF SORPTION ENERGTICS FOR HYDROPHOBIC ORGANIC CHEMICALS BY SYNTHETIC AND NATURAL SORBENTS FROM METHANOL/WATER SOLVENT MIXTURES

EPA Science Inventory

Reversed-phase liquid chromatography (RPLC) was used to investigate the thermodynamics and mechanisms of hydrophobic organic chemical (HOC) retention from methanol/water solvent mixtures. The enthalpy-entropy compensation model was used to infer that the hydro- phobic sorptive me...

The solvation of L-serine in mixtures of water with some aprotic solvents at 298.15 K

NASA Astrophysics Data System (ADS)

Mezhevoi, I. N.; Badelin, V. G.

2009-03-01

The integral enthalpies of solution Δsol H m of L-serine in mixtures of water with acetonitrile, 1,4-dioxane, dimethylsulfoxide (DMSO), and acetone were measured by solution calorimetry at organic component concentrations up to 0.31 mole fractions. The standard enthalpies of solution (Δsol H°), transfer (Δtr H°), and solvation (Δsolv H°) of L-serine from water into mixed solvents were calculated. The dependences of Δsol H°, Δsolv H°, and Δtr H° on the composition of aqueous-organic solvents contained extrema. The calculated enthalpy coefficients of pair interactions of the amino acid with cosolvent molecules were positive and increased in the series acetonitrile, 1,4-dioxane, DMSO, acetone. The results obtained were interpreted from the point of view of various types of interactions in solutions and the influence of the nature of organic solvents on the thermochemical characteristics of solutions.

Health assessment for Pasley Solvents and Chemical, Garden City, New York, Region 2. CERCLIS No. NYD991292004. Preliminary report

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

Not Available

1989-06-01

The Pasley Solvents and Chemicals site, a National Priorities List site, is located in the Town of Hempstead, immediately east of the Village of Garden City in Nassau County, New York. Between 1969 and 1982, Pasley operated a chemical distribution facility on the lot, occasionally storing waste chemicals. Prior to this, Commander Oil used the site for gasoline storage and fuel oil distribution. The Nassau County Health Department (NCHD) investigated the site in 1981 and found the on-site soil and ground water to be contaminated with organic solvents and petroleum products. On-site sampling by NCHD and the owner has revealedmore » organic chemicals and petroleum products in both soil and ground water. Six chlorinated solvents and four aromatic compounds are in ground water above the part per million. The site is a potential threat to public health.« less

A Coarse-Grained Protein Model in a Water-like Solvent

NASA Astrophysics Data System (ADS)

Sharma, Sumit; Kumar, Sanat K.; Buldyrev, Sergey V.; Debenedetti, Pablo G.; Rossky, Peter J.; Stanley, H. Eugene

2013-05-01

Simulations employing an explicit atom description of proteins in solvent can be computationally expensive. On the other hand, coarse-grained protein models in implicit solvent miss essential features of the hydrophobic effect, especially its temperature dependence, and have limited ability to capture the kinetics of protein folding. We propose a free space two-letter protein (``H-P'') model in a simple, but qualitatively accurate description for water, the Jagla model, which coarse-grains water into an isotropically interacting sphere. Using Monte Carlo simulations, we design protein-like sequences that can undergo a collapse, exposing the ``Jagla-philic'' monomers to the solvent, while maintaining a ``hydrophobic'' core. This protein-like model manifests heat and cold denaturation in a manner that is reminiscent of proteins. While this protein-like model lacks the details that would introduce secondary structure formation, we believe that these ideas represent a first step in developing a useful, but computationally expedient, means of modeling proteins.

Structure and dynamics of phosphate ion in aqueous solution: an ab initio QMCF MD study.

PubMed

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.

ABIOTIC REACTIONS MAY BE THE MOST IMPORTANT MECHANISM IN NATURAL ATTENUATION OF CHLORINATED SOLVENTS

EPA Science Inventory

The EPA Technical Protocol for Evaluating Natural Attenuation of Chlorinated Solvents in Ground Water was developed with the assumption that natural biological reductive dechlorination was the only important mechanism for destruction of chlorinated solvents and their reduction ...

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

PubMed

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

2001-12-05

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

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

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

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

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

Process for removing polychlorinated biphenyls from soil

DOEpatents

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

1984-11-16

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

Effect of solvents on the enzyme mediated degradation of copolymers

NASA Astrophysics Data System (ADS)

Banerjee, Aditi; Chatterjee, Kaushik; Madras, Giridhar

2015-09-01

The biodegradation of polycaprolactone (PCL), polylactic acid (PLA), polyglycolide (PGA) and their copolymers, poly (lactide-co-glycolide) and poly (D, L-lactide-co-caprolactone) (PLCL) was investigated. The influence of different solvents on the degradation of these polymers at 37 °C in the presence of two different lipases namely Novozym 435 and the free lipase of porcine pancreas was investigated. The rate coefficients for the polymer degradation and enzyme deactivation were determined using continuous distribution kinetics. Among the homopolymers, the degradation of PGA was nearly an order of magnitude lower than that for PCL and PLA. The overall rate coefficients of the copolymers were higher than their respective homopolymers. Thus, PLCL degraded faster than either PCL or PLA. The degradation was highly dependent on the viscosity of the solvent used with the highest degradation observed in acetone. The degradation of the polymers in acetone was nearly twice that observed in dimethyl sulfoxide indicating that the degradation decreases with increase in the solvent viscosity. The degradation of the polymers in water-solvent mixtures indicated an optimal water content of 2.5 wt% of water.

Strong impact of the solvent on the photokinetics of a 2(1H)-pyrimidinone.

PubMed

Ryseck, G; Villnow, T; Hugenbruch, S; Schaper, K; Gilch, P

2013-08-01

Pyrimidinones are part of the (6-4) photolesions which may be formed from two pyrimidine bases adjacent on a DNA strand. In relation to the secondary photochemistry of the (6-4) lesion, i.e. its transformation into a Dewar valence isomer, photophysical and photochemical properties of 1-methyl-2(1H)-pyrimidinone (1MP) in water, acetonitrile, methanol, and 1,4-dioxane are reported here. As deduced from steady state fluorescence and femtosecond transient absorption spectroscopy the S1 lifetime of 1MP is strongly affected by the solvent. The lifetimes range from 400 ps for water to 40 ps for 1,4-dioxane. Internal conversion (IC) and intersystem crossing (ISC) contribute to the S1 decay. The solvent effect on the IC rate constant is more pronounced than on the ISC constant. The quantum yields for the consumption of 1MP (values for nitrogen purged solvents) are large for methanol (0.35) and 1,4-dioxane (0.24) and small for acetonitrile (0.02) and water (0.003). Hydrogen abstraction from the solvent by the triplet state of 1MP may rationalize this.

Femtosecond dynamics in hydrogen-bonded solvents

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

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

1993-09-01

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

Effect of solvents on the electrochemical properties of binder-free sulfur cathode films in lithium–sulfur batteries

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

Ryu, Ho-Suk; Kim, Byeong-Wook; Park, Jin-Woo

Highlights: • The binder-free sulfur electrode with high sulfur contents of 75 wt.% was fabricated. • The binder-free sulfur electrode using NMP solvents showed 784 mAh g{sup −1} after 40 cycles. • The solvent affect the electrochemical properties of binder-free sulfur electrode films. - Abstract: The effects of solvents on the preparation of sulfur cathodes were investigated by fabricating binder-free sulfur electrode films using three different solvents: 1-methyl-2-pyrrolidinone (NMP), acetonitrile, and deionized water. These solvents are commonly employed to dissolve binders used to prepare sulfur cathodes for lithium–sulfur batteries. The sulfur electrode fabricated with NMP had a higher discharge capacitymore » and longer cycle life than the ones fabricated with acetonitrile and deionized water. Better adhesion between the current collector and the sulfur electrode accounted for the improved capacity and cycle life of the battery. In addition, the stability of the electrode in the electrolyte was a result of the solubility of sulfur in the solvent. We thus concluded that the solvents used in the fabrication of sulfur electrodes had a positive influence on the electrochemical properties of Li–S batteries.« less

Effects of water-alcohol binary solvents on the thermochemical characteristics of L-tryptophane dissolution at 298.15 K

NASA Astrophysics Data System (ADS)

Badelin, V. G.; Smirnov, V. I.

2013-01-01

The enthalpies of L-tryptophane solution in water-methanol, water-ethanol, water-1-propanol, and water-2-propanol mixtures at alcohol concentrations of x 2 = 0-0.4 mole fractions were measured by calorimetry. The standard enthalpies of L-tryptophane solution (Δsol H ∘) and transfer (Δtr H ∘) from water to the binary solvent were calculated. The influence of the composition of the water-alcohol mixture and the structure and properties of L-tryptophane on the enthalpy characteristics of the latter was considered. The enthalpy coefficients of pair interactions ( h xy ) of L-tryptophane with alcohol molecules were calculated. The coefficients were positive and increased in the series: methanol (MeOH), ethanol (EtOH), 1-propanol (1-PrOH), and 2-propanol (2-PrOH). The solution and transfer enthalpies of L-tryptophane were compared with those of aliphatic amino acids (glycine, L-threonine, DL-alanine, L-valine, and L-phenylalanine) in similar binary solvents.

Green technology approach towards herbal extraction method

NASA Astrophysics Data System (ADS)

Mutalib, Tengku Nur Atiqah Tengku Ab; Hamzah, Zainab; Hashim, Othman; Mat, Hishamudin Che

2015-05-01

The aim of present study was to compare maceration method of selected herbs using green and non-green solvents. Water and d-limonene are a type of green solvents while non-green solvents are chloroform and ethanol. The selected herbs were Clinacanthus nutans leaf and stem, Orthosiphon stamineus leaf and stem, Sesbania grandiflora leaf, Pluchea indica leaf, Morinda citrifolia leaf and Citrus hystrix leaf. The extracts were compared with the determination of total phenolic content. Total phenols were analyzed using a spectrophotometric technique, based on Follin-ciocalteau reagent. Gallic acid was used as standard compound and the total phenols were expressed as mg/g gallic acid equivalent (GAE). The most suitable and effective solvent is water which produced highest total phenol contents compared to other solvents. Among the selected herbs, Orthosiphon stamineus leaves contain high total phenols at 9.087mg/g.

Influence of solvent on micellar morphologies of semifluorinated block copolymers.

PubMed

Lee, Min Young; Kim, Sang Jae; Jeong, Yeon Tae; Kim, Joo Hyun; Gal, Yeong-Soon; Lim, Kwon Taek

2009-12-01

The influence of solvents on micellar architectures of block copolymers composed of poly(1H,1H-dihydroperfluorooctyl methacrylate) and poly(ethylene oxide) was investigated. In this study, binary solvents with desired proportions were chosen, which had remarkable influence on the morphology of the resulting micelles. With simple adjusting the composition of the binary solvent of chloroform and trichlorofluoromethane, interesting shapes of micelle-like aggregates, such as core-shell, cylinder, worm-like and inverted micelles were formed with sizes of 15, 70, 30 and 250 nm, respectively. In the case of methanol/water system, core-shell spheres and vesicles were produced by varying the proportion of the contents. The morphologies were also tuned to honeycomb-like and bowl-shaped micelles as well as large planar lamellae with holes in DMF and water binary solvent.

Cooperative effects in the structuring of fluoride water clusters: Ab initio hybrid quantum mechanical/molecular mechanical model incorporating polarizable fluctuating charge solvent

NASA Astrophysics Data System (ADS)

Bryce, Richard A.; Vincent, Mark A.; Malcolm, Nathaniel O. J.; Hillier, Ian H.; Burton, Neil A.

1998-08-01

A new hybrid quantum mechanical/molecular mechanical model of solvation is developed and used to describe the structure and dynamics of small fluoride/water clusters, using an ab initio wave function to model the ion and a fluctuating charge potential to model the waters. Appropriate parameters for the water-water and fluoride-water interactions are derived, with the fluoride anion being described by density functional theory and a large Gaussian basis. The role of solvent polarization in determining the structure and energetics of F(H2O)4- clusters is investigated, predicting a slightly greater stability of the interior compared to the surface structure, in agreement with ab initio studies. An extended Lagrangian treatment of the polarizable water, in which the water atomic charges fluctuate dynamically, is used to study the dynamics of F(H2O)4- cluster. A simulation using a fixed solvent charge distribution indicates principally interior, solvated states for the cluster. However, a preponderance of trisolvated configurations is observed using the polarizable model at 300 K, which involves only three direct fluoride-water hydrogen bonds. Ab initio calculations confirm this trisolvated species as a thermally accessible state at room temperature, in addition to the tetrasolvated interior and surface structures. Extension of this polarizable water model to fluoride clusters with five and six waters gave less satisfactory agreement with experimental energies and with ab initio geometries. However, our results do suggest that a quantitative model of solvent polarization is fundamental for an accurate understanding of the properties of anionic water clusters.

Microscopic relaxations in a protein sustained down to 160K in a non-glass forming organic solvent.

PubMed

Mamontov, E; O'Neill, H

2017-01-01

We have studied microscopic dynamics of a protein in carbon disulfide, a non-glass forming solvent, down to its freezing temperature of ca. 160K. We have utilized quasielastic neutron scattering. A comparison of lysozyme hydrated with water and dissolved in carbon disulfide reveals a stark difference in the temperature dependence of the protein's microscopic relaxation dynamics induced by the solvent. In the case of hydration water, the common protein glass-forming solvent, the protein relaxation slows down in response to a large increase in the water viscosity on cooling down, exhibiting a well-known protein dynamical transition. The dynamical transition disappears in non-glass forming carbon disulfide, whose viscosity remains a weak function of temperature all the way down to freezing at just below 160K. The microscopic relaxation dynamics of lysozyme dissolved in carbon disulfide is sustained down to the freezing temperature of its solvent at a rate similar to that measured at ambient temperature. Our results demonstrate that protein dynamical transition is not merely solvent-assisted, but rather solvent-induced, or, more precisely, is a reflection of the temperature dependence of the solvent's glass-forming dynamics. We hypothesize that, if the long debated idea regarding the direct link between the microscopic relaxations and the biological activity in proteins is correct, then not only the microscopic relaxations, but also the activity, could be sustained in proteins all the way down to the freezing temperature of a non-glass forming solvent with a weak temperature dependence of its viscosity. This article is part of a Special Issue entitled "Science for Life" Guest Editor: Dr. Austen Angell, Dr. Salvatore Magazù and Dr. Federica Migliardo. Copyright © 2016 Elsevier B.V. All rights reserved.

Solidification of floating organic droplet in dispersive liquid-liquid microextraction as a green analytical tool.

PubMed

Mansour, Fotouh R; Danielson, Neil D

2017-08-01

Dispersive liquid-liquid microextraction (DLLME) is a special type of microextraction in which a mixture of two solvents (an extracting solvent and a disperser) is injected into the sample. The extraction solvent is then dispersed as fine droplets in the cloudy sample through manual or mechanical agitation. Hence, the sample is centrifuged to break the formed emulsion and the extracting solvent is manually separated. The organic solvents commonly used in DLLME are halogenated hydrocarbons that are highly toxic. These solvents are heavier than water, so they sink to the bottom of the centrifugation tube which makes the separation step difficult. By using solvents of low density, the organic extractant floats on the sample surface. If the selected solvent such as undecanol has a freezing point in the range 10-25°C, the floating droplet can be solidified using a simple ice-bath, and then transferred out of the sample matrix; this step is known as solidification of floating organic droplet (SFOD). Coupling DLLME to SFOD combines the advantages of both approaches together. The DLLME-SFOD process is controlled by the same variables of conventional liquid-liquid extraction. The organic solvents used as extractants in DLLME-SFOD must be immiscible with water, of lower density, low volatility, high partition coefficient and low melting and freezing points. The extraction efficiency of DLLME-SFOD is affected by types and volumes of organic extractant and disperser, salt addition, pH, temperature, stirring rate and extraction time. This review discusses the principle, optimization variables, advantages and disadvantages and some selected applications of DLLME-SFOD in water, food and biomedical analysis. Copyright © 2017 Elsevier B.V. All rights reserved.

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

USGS Publications Warehouse

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

1990-01-01

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

Solubility behavior of lamivudine crystal forms in recrystallization solvents.

PubMed

Jozwiakowski, M J; Nguyen, N A; Sisco, J M; Spancake, C W

1996-02-01

Lamivudine can be obtained as acicular crystals (form I, 0.2 hydrate) from water or methanol and as bipyramidal crystals (form II, nonsolvated) from many nonaqueous solvents. Form II is thermodynamically favored in the solid state (higher melting point and greater density than form I) at ambient relative humidities. Solubility measurements on both forms versus solvent and temperature was used to determine whether entropy or enthalpy was the driving force for solubility. Solution calorimetry data indicated that form I is favored (less soluble) in all solvents studied on the basis of enthalpy alone. In higher alcohols and other organic solvents, form I has a larger entropy of solution than form II, which compensates for the enthalpic factors and results in physical stability for form II in these systems. The metastable crystal form solubility at 25 degrees C was estimated to be 1.2-2.3 times as high as the equilibrium solubility of the stable form, depending on the temperature, solvent, and crystal form. Binary solvent studies showed that > 18-20% water must be present in ethanol to convert the excess solid to form I at equilibrium.

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.

A molecular dynamics study of intramolecular proton transfer reaction of malonaldehyde in solution based upon a mixed quantum-classical approximation. II. Proton transfer reaction in non-polar solvent

NASA Astrophysics Data System (ADS)

Kojima, H.; Yamada, A.; Okazaki, S.

2015-05-01

The intramolecular proton transfer reaction of malonaldehyde in neon solvent has been investigated by mixed quantum-classical molecular dynamics (QCMD) calculations and fully classical molecular dynamics (FCMD) calculations. Comparing these calculated results with those for malonaldehyde in water reported in Part I [A. Yamada, H. Kojima, and S. Okazaki, J. Chem. Phys. 141, 084509 (2014)], the solvent dependence of the reaction rate, the reaction mechanism involved, and the quantum effect therein have been investigated. With FCMD, the reaction rate in weakly interacting neon is lower than that in strongly interacting water. However, with QCMD, the order of the reaction rates is reversed. To investigate the mechanisms in detail, the reactions were categorized into three mechanisms: tunneling, thermal activation, and barrier vanishing. Then, the quantum and solvent effects were analyzed from the viewpoint of the reaction mechanism focusing on the shape of potential energy curve and its fluctuations. The higher reaction rate that was found for neon in QCMD compared with that found for water solvent arises from the tunneling reactions because of the nearly symmetric double-well shape of the potential curve in neon. The thermal activation and barrier vanishing reactions were also accelerated by the zero-point energy. The number of reactions based on these two mechanisms in water was greater than that in neon in both QCMD and FCMD because these reactions are dominated by the strength of solute-solvent interactions.

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.

Effect of reaction solvent on hydroxyapatite synthesis in sol-gel process

NASA Astrophysics Data System (ADS)

Nazeer, Muhammad Anwaar; Yilgor, Emel; Yagci, Mustafa Baris; Unal, Ugur; Yilgor, Iskender

2017-12-01

Synthesis of hydroxyapatite (HA) through sol-gel process in different solvent systems is reported. Calcium nitrate tetrahydrate (CNTH) and diammonium hydrogen phosphate (DAHP) were used as calcium and phosphorus precursors, respectively. Three different synthesis reactions were carried out by changing the solvent media, while keeping all other process parameters constant. A measure of 0.5 M aqueous DAHP solution was used in all reactions while CNTH was dissolved in distilled water, tetrahydrofuran (THF) and N,N-dimethylformamide (DMF) at a concentration of 0.5 M. Ammonia solution (28-30%) was used to maintain the pH of the reaction mixtures in the 10-12 range. All reactions were carried out at 40 ± 2°C for 4 h. Upon completion of the reactions, products were filtered, washed and calcined at 500°C for 2 h. It was clearly demonstrated through various techniques that the dielectric constant and polarity of the solvent mixture strongly influence the chemical structure and morphological properties of calcium phosphate synthesized. Water-based reaction medium, with highest dielectric constant, mainly produced β-calcium pyrophosphate (β-CPF) with a minor amount of HA. DMF/water system yielded HA as the major phase with a very minor amount of β-CPF. THF/water solvent system with the lowest dielectric constant resulted in the formation of pure HA.

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

PubMed

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

2010-04-08

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

Viscoelastic stability of resin-composites aged in food-simulating solvents.

PubMed

Marghalani, Hanadi Y; Watts, David C

2013-09-01

To study time-dependent viscoelastic deformation (creep and recovery) of resin-composites, after conditioning in food-simulating solvents, under a compressive stress at 37°C. Five dimethacrylate-based composites: (Spectrum TPH, Premise Body, Tetric Ceram HB, Filtek P60, X-tra fil), and two Ormocers (Experimental Ormocer V 28407, Admira) were studied. Three groups of cylindrical specimens (4mm×6mm) were prepared and then conditioned in 3 solvents: methyl ethyl ketone (MEK), ethanol, and water for 1 month at 37°C. The compressive creep-strain under 35MPa in 37°C water was recorded continuously for 2h and then the unloaded recovery-strain was monitored for another 2h. The data were analyzed by one-way ANOVA and Bonferroni's test. The materials all exhibited classic creep and recovery curves, with most parameters being significantly different (p<0.0001) for each solvent condition. All materials showed lower creep-strain in water than in ethanol or MEK solvents. Maximum creep-strain and permanent-set gave negative linear-regression (r(2)>0.98) with logarithm of the solvent solubility-parameter. The % mean (SD) creep-strain ranged from a minimum of 0.82 (0.01) for the Exp. Ormocer in water to the maximum of 4.19 (0.30) for Admira in MEK. Similar trends were found for permanent-set. The dimethacrylate-based composites behaved as an intermediate group, apart from X-tra fil that had similar stability to the Exp. Ormocer. The viscoelastic stability (low creep and permanent-set) of the Exp. Ormocer, compared to many dimethacrylate-based composites, in food-simulating solvents may be due to its diluent-free formulation. This was closely matched by a highly-filled dimethacrylate material (X-tra fil). Copyright © 2013 Academy of Dental Materials. All rights reserved.

Lid dynamics of porcine pancreatic lipase in non-aqueous solvents.

PubMed

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.

Human telomere sequence DNA in water-free and high-viscosity solvents: G-quadruplex folding governed by Kramers rate theory.

PubMed

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.

Vibrational spectroscopic determination of local solvent electric field, solute-solvent electrostatic interaction energy, and their fluctuation amplitudes.

PubMed

Lee, Hochan; Lee, Gayeon; Jeon, Jonggu; Cho, Minhaeng

2012-01-12

IR probes have been extensively used to monitor local electrostatic and solvation dynamics. Particularly, their vibrational frequencies are highly sensitive to local solvent electric field around an IR probe. Here, we show that the experimentally measured vibrational frequency shifts can be inversely used to determine local electric potential distribution and solute-solvent electrostatic interaction energy. In addition, the upper limits of their fluctuation amplitudes are estimated by using the vibrational bandwidths. Applying this method to fully deuterated N-methylacetamide (NMA) in D(2)O and examining the solvatochromic effects on the amide I' and II' mode frequencies, we found that the solvent electric potential difference between O(═C) and D(-N) atoms of the peptide bond is about 5.4 V, and thus, the approximate solvent electric field produced by surrounding water molecules on the NMA is 172 MV/cm on average if the molecular geometry is taken into account. The solute-solvent electrostatic interaction energy is estimated to be -137 kJ/mol, by considering electric dipole-electric field interaction. Furthermore, their root-mean-square fluctuation amplitudes are as large as 1.6 V, 52 MV/cm, and 41 kJ/mol, respectively. We found that the water electric potential on a peptide bond is spatially nonhomogeneous and that the fluctuation in the electrostatic peptide-water interaction energy is about 10 times larger than the thermal energy at room temperature. This indicates that the peptide-solvent interactions are indeed important for the activation of chemical reactions in aqueous solution.

The fifth solvatomorph of gallic acid with a supramolecular channel structure: Structural complexity and phase transitions

NASA Astrophysics Data System (ADS)

Thomas, Sajesh P.; Kaur, Ramanpreet; Kaur, Jassjot; Sankolli, Ravish; Nayak, Susanta K.; Guru Row, Tayur N.

2013-01-01

A new solvatomorph of gallic acid was generated using chiral additive technique and characterized by single crystal and powder X-ray diffraction, C-13 NMR, IR spectroscopic techniques and thermal analysis. The supramolecular channels formed by hexameric motifs of gallic acid and solvent molecules contain highly disordered solvent molecules with fractional occupancies.

Switchable polarity solvent for liquid phase microextraction of Cd(II) as pyrrolidinedithiocarbamate chelates from environmental samples.

PubMed

Yilmaz, Erkan; Soylak, Mustafa

2015-07-30

A switchable polarity solvent was synthesized from triethylamine (TEA)/water/CO2 (Dry ice) via proton transfer reaction has been used for the microextraction of cadmium(II) as pyrrolidinedithiocarbamate (APDC) chelate. Cd(II)-APDC chelate was extracted into the switchable polarity solvent drops by adding 2 mL 10 M sodium hydroxide solution. Analytical parameters affecting the complex formation and microextraction efficiency such as pH, amount of ligand, volume of switchable polarity solvent and NaOH, sample volume were optimized. The effects of foreign ions were found tolerably. Under optimum conditions, the detection limit was 0.16 μg L(-1) (3Sb/m, n = 7) and the relative standard deviation was 5.4% (n = 7). The method was validated by the analysis of certified reference materials (TMDA-51.3 fortified water, TMDA-53.3 fortified water and SPS-WW2 waste water, 1573a Tomato Leaves and Oriental Basma Tobacco Leaves (INCT-OBTL-5)) and addition/recovery tests. The method was successfully applied to determination of cadmium contents of water, vegetable, fruit and cigarette samples. Copyright © 2015 Elsevier B.V. All rights reserved.

Characterization of 2-(2-Methoxyethoxy)ethanol Substituted Phosphazene Polymers Using Pervaporation, Solubility Parameters and Sorption Studies

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

Orme, Christopher Joseph; Klaehn, John Ray; Harrup, Mason Kurt

Two linear phosphazene polymers were synthesized with differing amounts of hydrophilic 2-(2-methoxyethoxy)ethanol (MEE) and hydrophobic 4-methoxyphenol (MEOP) substituted on the backbone. These high polymers were cast into membranes and their permeability to water, methanol, ethanol, and 2-propanol was evaluated as a function of temperature. An additional polymer with a low content of MEE was studied for water permeation and was characterized by trace flux. At higher levels of MEE on the backbone, fluxes of all solvents increased. Solubility also was found to increase with increasing MEE content for all solvents except water. Unexpectedly, water was found to be less solublemore » in the higher MEE polymer, although higher membrane fluxes were observed. Diffusion coefficients showed the following trend: methanol 2-propanol > ethanol water. Finally, the affinity of solvents and polymers was discussed in terms of Hansen solubility parameters.« less

High mobility organic field-effect transistor based on water-soluble deoxyribonucleic acid via spray coating

NASA Astrophysics Data System (ADS)

Shi, Wei; Han, Shijiao; Huang, Wei; Yu, Junsheng

2015-01-01

High mobility organic field-effect transistors (OFETs) by inserting water-soluble deoxyribonucleic acid (DNA) buffer layer between electrodes and pentacene film through spray coating process were fabricated. Compared with the OFETs incorporated with DNA in the conventional organic solvents of ethanol and methanol: water mixture, the water-soluble DNA based OFET exhibited an over four folds enhancement of field-effect mobility from 0.035 to 0.153 cm2/Vs. By characterizing the surface morphology and the crystalline structure of pentacene active layer through atomic force microscope and X-ray diffraction, it was found that the adoption of water solvent in DNA solution, which played a key role in enhancing the field-effect mobility, was ascribed to both the elimination of the irreversible organic solvent-induced bulk-like phase transition of pentacene film and the diminution of a majority of charge trapping at interfaces in OFETs.

Excited state electronic polarization and reappraisal of the n ← π∗ emission of acetone in water

NASA Astrophysics Data System (ADS)

Orozco-González, Yoelvis; Coutinho, Kaline; Canuto, Sylvio

2010-10-01

Electronic polarization of the acetone molecule in the excited n → π∗ state is considered and its influence on the solvent shift in the emission spectrum is analyzed. Using an iterative procedure the electronic polarizations of both the ground and the excited states are included and compared with previous results obtained with Car-Parrinello dynamics. Analysis of the emission transition obtained using CIS(D)/aug-cc-pVDZ on statistically uncorrelated solute-solvent structures, composed of acetone and twelve explicit water molecules embedded in the electrostatic field of remaining 263 water molecules, corroborates that the solvent effect is mild, calculated here between 80 and 380 cm -1.

Molecular dynamics simulations to study the solvent influence on protein structure

NASA Astrophysics Data System (ADS)

Dominguez, Hector

2016-05-01

Molecular simulations were carried out to study the influence of different water models in two protein systems. Most of the solvents used in protein simulations, e.g., SPC/E or TIP3P, fail to reproduce the bulk water static dielectric constant. Recently a new water model, TIP4P/ɛ, which reproduces the experimental dielectric constant was reported. Therefore, simulations for two different proteins, Lysozyme and Ubiquitin with SPC/E, TIP3P and TIP4P/ɛ solvents were carried out. Dielectric constants and structural properties were calculated and comparisons were conducted. The structural properties between the three models are very similar, however, the dielectric constants are different in each case.

Temporal variation of VOC emission from solvent and water based wood stains

NASA Astrophysics Data System (ADS)

de Gennaro, Gianluigi; Loiotile, Annamaria Demarinis; Fracchiolla, Roberta; Palmisani, Jolanda; Saracino, Maria Rosaria; Tutino, Maria

2015-08-01

Solvent- and water-based wood stains were monitored using a small test emission chamber in order to characterize their emission profiles in terms of Total and individual VOCs. The study of concentration-time profiles of individual VOCs enabled to identify the compounds emitted at higher concentration for each type of stain, to examine their decay curve and finally to estimate the concentration in a reference room. The solvent-based wood stain was characterized by the highest Total VOCs emission level (5.7 mg/m3) that decreased over time more slowly than those related to water-based ones. The same finding was observed for the main detected compounds: Benzene, Toluene, Ethylbenzene, Xylenes, Styrene, alpha-Pinene and Camphene. On the other hand, the highest level of Limonene was emitted by a water-based wood stain. However, the concentration-time profile showed that water-based product was characterized by a remarkable reduction of the time of maximum and minimum emission: Limonene concentration reached the minimum concentration in about half the time compared to the solvent-based product. According to AgBB evaluation scheme, only one of the investigated water-based wood stains can be classified as a low-emitting product whose use may not determine any potential adverse effect on human health.

Monitoring trihalomethanes in chlorinated waters using a dispersive liquid-liquid microextraction method with a non-chlorinated organic solvent and gas chromatography-mass spectrometry.

PubMed

Pacheco-Fernández, Idaira; Herrera-Fuentes, Ariadna; Delgado, Bárbara; Pino, Verónica; Ayala, Juan H; Afonso, Ana M

2017-03-01

The environmental monitoring of trihalomethanes (THMs) has been performed by setting up a dispersive liquid-liquid microextraction method in combination with gas chromatography (GC)-mass spectrometry (MS). The optimized method only requires ∼26 µL of decanol as extractant solvent, dissolved in ∼1 mL of acetone (dispersive solvent) for 5 mL of the environmental water containing THMs. The mixture is then subjected to vortex for 1 min and then centrifuged for 2 min at 3500 rpm. The microdroplet containing the extracted THMs is then sampled with a micro-syringe, and injected (1 µL) in the GC-MS. The method is characterized for being fast (3 min for the entire sample preparation step) and environmentally friendly (low amounts of solvents required, being all non-chlorinated), and also for getting average relative recoveries of 90.2-106% in tap waters; relative standard deviation values always lower than 11%; average enrichment factors of 48-49; and detection limits down to 0.7 µg·L-1. Several waters: tap waters, pool waters, and wastewaters were successfully analyzed with the method proposed. Furthermore, the method was used to monitor the formation of THMs in wastewaters when different chlorination parameters, namely temperature and pH, were varied.

The Electrocatalytic Reduction of Carbon Dioxide Using Macrocycles of Nickel and Cobalt.

DTIC Science & Technology

1980-10-24

34 water only. Carbon monoxide was found to coprise at least 50% of the total reduced products in all cases; H was also produced in most cases. While a...experiments performed in a gas tight elec- trolysis cell followed by g.c. analysis. The solvents used were either CH3CN-H20 or water only. Carbon...these experiments, and the solvent systems used were either acetonitrile/ water or water only. Gas chromato- graphic analysis was used to determine

Interaction between morin and AOT reversed micelles--studies with UV-vis at 25 °C.

PubMed

Bhattarai, Ajaya; Wilczura-Wachnik, H

2014-01-30

The precise measurements of morin absorbance in presence of surfactant/solvent/water systems at 25 °C by UV-vis technique are reported. The surfactant used in presented study was sodium bis(2-ethylhexyl) sulfosuccinate called Aerosol-OT or AOT. The solvents selected were: ethanol, ethylene glycol, and n-decanol. The concentrations of AOT were varied between 0.001 and 0.4 mol/kg. Morin concentration in quvette during UV-vis registration was not equals in all solvent because of its different solubility and absorption intensity depending on the solvent. Water concentration in the studied systems was defined by R parameter according to relation: R=[H2O]/[AOT] and was equal 0, 30 and 40 in ethanol; 0, 10, 20 and 30 in ethylene glycol and 0, 10, 20, 30, and 40 in n-decanol. In presented work a Nernstian distribution of morin between the organic and micellar phases was assumed. The intensity of morin absorbance as a function of AOT concentration was analyzed. Using Non-linear Regression Procedure (NLREG) morin binding constant (K' [mol/kg]), and morin distribution constant (K) between organic phase and AOT micellar phase have been calculated. The experimental results have shown a significant influence of solvent, surfactant and water presence on morin UV-vis spectrum. Calculated data pointed out on different transfer of morin molecules from the organic to micellar phase depending on the solvent. Moreover, results of calculations indicate on competition between morin and water molecules interacting with AOT polar heads. Morin molecules privileged location in AOT reversed micelles strongly depends on the solvent. In case of systems with ethylene glycol as solvent is possible morin molecules location in polar cores of AOT reversed micelles as results of strong interaction between AOT polar heads and morin hydroxyl groups, whereas in case of ethanol and n-decanol morin molecules are located in palisade layer. Copyright © 2013 Elsevier B.V. All rights reserved.

Differentiation of Chemical Components in a Binary Solvent Vapor Mixture Using Carbon/Polymer Composite-Based Chemiresistors

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

Patel, Sanjay V.; Jenkins, Mark W.; Hughes, Robert C.

1999-07-19

We demonstrate a ''universal solvent sensor'' constructed from a small array of carbon/polymer composite chemiresistors that respond to solvents spanning a wide range of Hildebrand volubility parameters. Conductive carbon particles provide electrical continuity in these composite films. When the polymer matrix absorbs solvent vapors, the composite film swells, the average separation between carbon particles increases, and an increase in film resistance results, as some of the conduction pathways are broken. The adverse effects of contact resistance at high solvent concentrations are reported. Solvent vapors including isooctane, ethanol, dlisopropyhnethylphosphonate (DIMP), and water are correctly identified (''classified'') using three chemiresistors, their compositemore » coatings chosen to span the full range of volubility parameters. With the same three sensors, binary mixtures of solvent vapor and water vapor are correctly classified, following classification, two sensors suffice to determine the concentrations of both vapor components. Polyethylene vinylacetate and polyvinyl alcohol (PVA) are two such polymers that are used to classify binary mixtures of DIMP with water vapor; the PVA/carbon-particle-composite films are sensitive to less than 0.25{degree}A relative humidity. The Sandia-developed VERI (Visual-Empirical Region of Influence) technique is used as a method of pattern recognition to classify the solvents and mixtures and to distinguish them from water vapor. In many cases, the response of a given composite sensing film to a binary mixture deviates significantly from the sum of the responses to the isolated vapor components at the same concentrations. While these nonlinearities pose significant difficulty for (primarily) linear methods such as principal components analysis, VERI handles both linear and nonlinear data with equal ease. In the present study the maximum speciation accuracy is achieved by an array containing three or four sensor elements, with the addition of more sensors resulting in a measurable accuracy decrease.« less

Free energetics of carbon nanotube association in aqueous inorganic NaI salt solutions: Temperature effects using all-atom molecular dynamics simulations.

PubMed

Ou, Shu-Ching; Cui, Di; Wezowicz, Matthew; Taufer, Michela; Patel, Sandeep

2015-06-15

In this study, we examine the temperature dependence of free energetics of nanotube association using graphical processing unit-enabled all-atom molecular dynamics simulations (FEN ZI) with two (10,10) single-walled carbon nanotubes in 3 m NaI aqueous salt solution. Results suggest that the free energy, enthalpy and entropy changes for the association process are all reduced at the high temperature, in agreement with previous investigations using other hydrophobes. Via the decomposition of free energy into individual components, we found that solvent contribution (including water, anion, and cation contributions) is correlated with the spatial distribution of the corresponding species and is influenced distinctly by the temperature. We studied the spatial distribution and the structure of the solvent in different regions: intertube, intratube and the bulk solvent. By calculating the fluctuation of coarse-grained tube-solvent surfaces, we found that tube-water interfacial fluctuation exhibits the strongest temperature dependence. By taking ions to be a solvent-like medium in the absence of water, tube-anion interfacial fluctuation shows similar but weaker dependence on temperature, while tube-cation interfacial fluctuation shows no dependence in general. These characteristics are discussed via the malleability of their corresponding solvation shells relative to the nanotube surface. Hydrogen bonding profiles and tetrahedrality of water arrangement are also computed to compare the structure of solvent in the solvent bulk and intertube region. The hydrophobic confinement induces a relatively lower concentration environment in the intertube region, therefore causing different intertube solvent structures which depend on the tube separation. This study is relevant in the continuing discourse on hydrophobic interactions (as they impact generally a broad class of phenomena in biology, biochemistry, and materials science and soft condensed matter research), and interpretations of hydrophobicity in terms of alternative but parallel signatures such as interfacial fluctuations, dewetting transitions, and enhanced fluctuation probabilities at interfaces. © 2015 Wiley Periodicals, Inc.

INFLUENCE OF SOLVENT AND SORBENT CHARACTERISTICS ON DISTRIBUTION OF PENTACHLOROPHENOL IN OCTANOL-WATER AND SOIL-WATER SYSTEMS

EPA Science Inventory

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...

Natural Attenuation of Chlorinated Solvents and Fuel Components (BTEX and MTBE) in Ground Water

EPA Science Inventory

Monitored Natural Attenuation is widely used in the USA to deal with ground water contamination from fuel components such as the BTEX compounds or MTBE or TBA and from chlorinated solvents such as PCE, TCE, and TCA. This presentation reviews the theory and practice of MNA in the...

Development of a Gas Chromatography/Mass Spectrometry Method for the Analysis of the Solvent Stabilizer 1,4-Dioxane in Drinking Water

EPA Science Inventory

The solvent stabilizer 1,4-dioxane was named to the latest draft Drinking Water Contaminant Candidate List (CCL3) in February 2008 by the United States Environmental Protection Agency (USEPA). To collect occurrence data under the Unregulated Contaminant Monitoring Regulation (UC...

Water Dynamics at Protein-Protein Interfaces: Molecular Dynamics Study of Virus-Host Receptor Complexes.

PubMed

Dutta, Priyanka; Botlani, Mohsen; Varma, Sameer

2014-12-26

The dynamical properties of water at protein-water interfaces are unlike those in the bulk. Here we utilize molecular dynamics simulations to study water dynamics in interstitial regions between two proteins. We consider two natural protein-protein complexes, one in which the Nipah virus G protein binds to cellular ephrin B2 and the other in which the same G protein binds to ephrin B3. While the two complexes are structurally similar, the two ephrins share only a modest sequence identity of ∼50%. X-ray crystallography also suggests that these interfaces are fairly extensive and contain exceptionally large amounts of waters. We find that while the interstitial waters tend to occupy crystallographic sites, almost all waters exhibit residence times of less than hundred picoseconds in the interstitial region. We also find that while the differences in the sequence of the two ephrins result in quantitative differences in the dynamics of interstitial waters, the trends in the shifts with respect to bulk values are similar. Despite the high wetness of the protein-protein interfaces, the dynamics of interstitial waters are considerably slower compared to the bulk-the interstitial waters diffuse an order of magnitude slower and have 2-3 fold longer hydrogen bond lifetimes and 2-1000 fold slower dipole relaxation rates. To understand the role of interstitial waters, we examine how implicit solvent models compare against explicit solvent models in producing ephrin-induced shifts in the G conformational density. Ephrin-induced shifts in the G conformational density are critical to the allosteric activation of another viral protein that mediates fusion. We find that in comparison with the explicit solvent model, the implicit solvent model predicts a more compact G-B2 interface, presumably because of the absence of discrete waters at the G-B2 interface. Simultaneously, we find that the two models yield strikingly different induced changes in the G conformational density, even for those residues whose conformational densities in the apo state are unaffected by the treatment of the bulk solvent. Together, these results show that the explicit treatment of interstitial water molecules is necessary for a proper description of allosteric transitions.

Mechanism of transport and distribution of organic solvents in blood

NASA Technical Reports Server (NTRS)

Lam, C. W.; Galen, T. J.; Boyd, J. F.; Pierson, D. L.

1990-01-01

Little is known about the mechanism of transport and distribution of volatile organic compounds in blood. Studies were conducted on five typical organic solvents to investigate how these compounds are transported and distributed in blood. Groups of four to five rats were exposed for 2 hr to 500 ppm of n-hexane, toluene, chloroform, methyl isobutyl ketone (MIBK), or diethyl ether vapor; 94, 66, 90, 51, or 49%, respectively, of these solvents in the blood were found in the red blood cells (RBCs). Very similar results were obtained in vitro when aqueous solutions of these solvents were added to rat blood. In vitro studies were also conducted on human blood with these solvents; 66, 43, 65, 49, or 46%, respectively, of the added solvent was taken up by the RBCs. These results indicate that RBCs from humans and rats exhibited substantial differences in affinity for the three more hydrophobic solvents studied. When solutions of these solvents were added to human plasma and RBC samples, large fractions (51-96%) of the solvents were recovered from ammonium sulfate-precipitated plasma proteins and hemoglobin. Smaller fractions were recovered from plasma water and red cell water. Less than 10% of each of the added solvents in RBC samples was found in the red cell membrane ghosts. These results indicate that RBCs play an important role in the uptake and transport of these solvents. Proteins, chiefly hemoglobin, are the major carriers of these compounds in blood. It can be inferred from the results of the present study that volatile lipophilic organic solvents are probably taken up by the hydrophobic sites of blood proteins.

Effect of spray-drying with organic solvents on the encapsulation, release and stability of fish oil.

PubMed

Encina, Cristian; Márquez-Ruiz, Gloria; Holgado, Francisca; Giménez, Begoña; Vergara, Cristina; Robert, Paz

2018-10-15

Fish-oil (FO) was encapsulated with hydroxypropylcelullose (HPC) by conventional spray-drying with water (FO-water) and solvent spray-drying with ethanol (FO-EtOH), methanol (FO-MeOH) and acetone (FO-Acet) in order to study the effect of the solvent on the encapsulation efficiency (EE), microparticle properties and stability of FO during storage at 40 °C. Results showed that FO-Acet presented the highest EE of FO (92.0%), followed by FO-EtOH (80.4%), FO-MeOH (75.0%) and FO-water (71.1%). A decrease of the dielectric constant increased the EE of FO, promoting triglyceride-polymer interactions instead of oil-in-water emulsion retention. FO release profile in aqueous model was similar for all FO-microparticles, releasing only the surface FO, according to Higuchi model. Oxidative stability of FO significantly improved by spray-drying with MeOH, both in surface and encapsulated oil fractions. In conclusion, encapsulation of FO by solvent spray-drying can be proposed as an alternative technology for encapsulation of hydrophobic molecules. Copyright © 2018 Elsevier Ltd. All rights reserved.

New methods for the analysis of the protein-solvent interface

NASA Astrophysics Data System (ADS)

Goodfellow, Julia M.; Pitt, William R.; Smart, Oliver S.; Williams, Mark A.

1995-09-01

The protein-solvent interface is complex and may include solvent channels and cavities as well as the normal surface water molecules. We describe several algorithms for investigating the intra- and inter-molecular interactions of proteins in general but with the aim of developing methods to accurately and definitively characterise the interactions of water and other small ligands with proteins. Specifically, we present the methods which underlie three programs (AQUARIUS2, HOLE and PRO_ACT) which can be used to to look at different aspects of these interactions.

Water-induced nanochannel networks in self-assembled block ionomers

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

Mineart, Kenneth P.; Al-Mohsin, Heba A.; Lee, Byeongdu

2016-03-07

Block ionomers cast from solution exhibit solvent-templated morphologies that can be altered by solvent-vapor annealing. When cast from a mixed solvent, a midblock-sulfonated pentablock ion- omer self-assembles into spherical ionic microdomains that are loosely connected. Upon exposure to liquid water, nanoscale channels irreversibly develop between the microdomains due to swelling and form a continuous mesoscale network. We use electron tomography and real-time X-ray scat- tering to follow this transformation and show that the resultant morphology provides a highly effec- tive diffusive pathway.

Technique for ultrasonic cleaning with volatile solvents eliminates need for hoods or condensers

NASA Technical Reports Server (NTRS)

Pipersky, E.

1969-01-01

Technique ultrasonically cleans small quantities of small mechanical parts in organic solvents without the need for vapor removal equipment. Parts are placed in a thin plastic bag with the solvent and then suspended in a cleaning tank containing the water-detergent solution.

Solvent-Free Synthesis of Zeolites: Mechanism and Utility.

PubMed

Wu, Qinming; Meng, Xiangju; Gao, Xionghou; Xiao, Feng-Shou

2018-05-08

Zeolites have been extensively studied for years in different areas of chemical industry, such as shape selective catalysis, ion-exchange, and gas adsorption and separation. Generally, zeolites are prepared from solvothermal synthesis in the presence of a large amounts of solvents such as water and alcohols in sealed autoclaves under autogenous pressure. Water has been regarded as essential to synthesize zeolites for fast mass transfer of reactants, but it occupies a large space in autoclaves, which greatly reduces the yield of zeolite products. Furthermore, polluted wastes and relatively high pressure due to the presence of water solvent in the synthesis also leads to environmental and safety issues. Recently, inspired by great benefits of solvent-free synthesis, including the environmental concerns, energy consumption, safety, and economic cost, researchers continually challenge the rationale of the solvent and reconsider the age-old question "Do we actually need solvents at all in zeolite synthesis?" In this Account, we briefly summarize our efforts to rationally synthesize zeolites via a solvent-free route. Our research demonstrates that a series of silica, aluminosilicate, and aluminophosphate-based zeolites can be successfully prepared by mixing, grinding, and heating starting solid materials under solvent-free conditions. Combining an organotemplate-free synthesis with a solvent-free approach maximizes the advantages resulting in a more sustainable synthetic route, which avoids using toxic and costly organic templates and the formation of harmful gases by calcination of organic templates at high temperature. Furthermore, new insights into the solvent-free crystallization process of zeolites have been provided by modern techniques such as NMR and UV-Raman spectroscopy, which should be helpful in designing new zeolite structures and developing novel routes for synthesis of zeolites. The role of water and the vital intermediates during the crystallization of zeolites have been proposed and verified. In addition to a significant reduction in liquid wastes and a remarkable increase in zeolite yields, the solvent-free synthesis of zeolites exhibits more unprecedented benefits, including (i) the formation of hierarchical micro-, meso-, and macrostructures, which benefit the mass transfer in the reactions, (ii) rapid synthesis at higher temperatures, which greatly improve the space-time yields of zeolites, and (iii) construction of a novel catalytic system for encapsulation of metal nanoparticles and metal oxide particles within zeolite crystals synergistically combining the advantages of catalytic metal nanoparticles and metal oxide particles (high activity) and zeolites (shape selectivity). We believe that the concept of "solvent-free synthesis of zeolites" would open a door for deep understanding of zeolite crystallization and the design of efficient zeolitic catalysts.

Effect of pigment concentration on fastness and color values of thermal and UV curable pigment printing

NASA Astrophysics Data System (ADS)

Baysal, Gulcin; Kalav, Berdan; Karagüzel Kayaoğlu, Burçak

2017-10-01

In the current study, it is aimed to determine the effect of pigment concentration on fastness and colour values of thermal and ultraviolet (UV) curable pigment printing on synthetic leather. For this purpose, thermal curable solvent-based and UV curable water-based formulations were prepared with different pigment concentrations (3, 5 and 7%) separately and applied by screen printing technique using a screen printing machine. Samples printed with solvent-based formulations were thermally cured and samples printed with water-based formulations were cured using a UV curing machine equipped with gallium and mercury (Ga/Hg) lamps at room temperature. The crock fastness values of samples printed with solvent-based formulations showed that increase in pigment concentration was not effective on both dry and wet crock fastness values. On the other hand, in samples printed with UV curable water-based formulations, dry crock fastness was improved and evaluated as very good for all pigment concentrations. However, increasing the pigment concentration affected the wet crock fastness values adversely and lower values were observed. As the energy level increased for each irradiation source, the fastness values were improved. In comparison with samples printed with solvent-based formulations, samples printed with UV curable water-based formulations yielded higher K/S values at all pigment concentrations. The results suggested that, higher K/S values can be obtained in samples printed with UV curable water-based formulations at a lower pigment concentration compared to samples printed with solvent-based formulations.

Micelle structure in a deep eutectic solvent: a small-angle scattering study.

PubMed

Sanchez-Fernandez, A; Edler, K J; Arnold, T; Heenan, R K; Porcar, L; Terrill, N J; Terry, A E; Jackson, A J

2016-05-18

In recent years many studies into green solvents have been undertaken and deep eutectic solvents (DES) have emerged as sustainable and green alternatives to conventional solvents since they may be formed from cheap non-toxic organic precursors. In this study we examine amphiphile behaviour in these novel media to test our understanding of amphiphile self-assembly within environments that have an intermediate polarity between polar and non-polar extremes. We have built on our recently published results to present a more detailed structural characterisation of micelles of sodium dodecylsulfate (SDS) within the eutectic mixture of choline chloride and urea. Here we show that SDS adopts an unusual cylindrical aggregate morphology, unlike that seen in water and other polar solvents. A new morphology transition to shorter aggregates was found with increasing concentration. The self-assembly of SDS was also investigated in the presence of water; which promotes the formation of shorter aggregates.

Method for producing metal oxide aerogels

DOEpatents

Tillotson, Thomas M.; Poco, John F.; Hrubesh, Lawrence W.; Thomas, Ian M.

1995-01-01

A two-step hydrolysis-condensation method was developed to form metal oxide aerogels of any density, including densities of less than 0.003g/cm.sup.3 and greater than 0.27g/cm.sup.3. High purity metal alkoxide is reacted with water, alcohol solvent, and an additive to form a partially condensed metal intermediate. All solvent and reaction-generated alcohol is removed, and the intermediate is diluted with a nonalcoholic solvent. The intermediate can be stored for future use to make aerogels of any density. The aerogels are formed by reacting the intermediate with water, nonalcoholic solvent, and a catalyst, and extracting the nonalcoholic solvent directly. The resulting monolithic aerogels are hydrophobic and stable under atmospheric conditions, and exhibit good optical transparency, high clarity, and homogeneity. The aerogels have high thermal insulation capacity, high porosity, mechanical strength and stability, and require shorter gelation times than aerogels formed by conventional methods.

Method for producing metal oxide aerogels

DOEpatents

Tillotson, T.M.; Poco, J.F.; Hrubesh, L.W.; Thomas, I.M.

1995-04-25

A two-step hydrolysis-condensation method was developed to form metal oxide aerogels of any density, including densities of less than 0.003g/cm{sup 3} and greater than 0.27g/cm{sup 3}. High purity metal alkoxide is reacted with water, alcohol solvent, and an additive to form a partially condensed metal intermediate. All solvent and reaction-generated alcohol is removed, and the intermediate is diluted with a nonalcoholic solvent. The intermediate can be stored for future use to make aerogels of any density. The aerogels are formed by reacting the intermediate with water, nonalcoholic solvent, and a catalyst, and extracting the nonalcoholic solvent directly. The resulting monolithic aerogels are hydrophobic and stable under atmospheric conditions, and exhibit good optical transparency, high clarity, and homogeneity. The aerogels have high thermal insulation capacity, high porosity, mechanical strength and stability, and require shorter gelation times than aerogels formed by conventional methods. 8 figs.

Enthalpy characteristics of the dissolution of L-valine in water/formamide mixtures at 298.15 K

NASA Astrophysics Data System (ADS)

Smirnov, V. I.; Badelin, V. G.

2016-11-01

The thermochemical dissolution of L-valine in solvent mixtures H2O + (formamide, N-methylformamide, and N, N-dimethylformamide) is studied at an organic component concentration of x 2 = 0-0.35 molar fractions and a temperature of 298.15 K. The experimental data are used to calculate standard enthalpies of dissolution, the transferring of L-valine from water to a mixed solvent, and the enthalpy coefficients of pairwise interactions ( h xy ) with organic solvent molecules. The correlation between the enthalpy characteristics of the dissolution of L-valine with the composition of aqueous organic mixtures and the nature of the organic solvent (its physicochemical properties) is determined. A comparative analysis of the values of h xy of a number of aliphatic L-amino acids in similar solvent mixtures with the hydrophobicity parameters of their side chains is performed.

Hemin-utilizing G-quadruplex DNAzymes are strongly active in organic co-solvents.

PubMed

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.

Microfluidic Extraction of Biomarkers using Water as Solvent

NASA Technical Reports Server (NTRS)

Amashukeli, Xenia; Manohara, Harish; Chattopadhyay, Goutam; Mehdi, Imran

2009-01-01

A proposed device, denoted a miniature microfluidic biomarker extractor (mu-EX), would extract trace amounts of chemicals of interest from samples, such as soils and rocks. Traditionally, such extractions are performed on a large scale with hazardous organic solvents; each solvent capable of dissolving only those molecules lying within narrow ranges of specific chemical and physical characteristics that notably include volatility, electric charge, and polarity. In contrast, in the mu-EX, extractions could be performed by use of small amounts (typically between 0.1 and 100 L) of water as a universal solvent. As a rule of thumb, in order to enable solvation and extraction of molecules, it is necessary to use solvents that have polarity sufficiently close to the polarity of the target molecules. The mu-EX would make selection of specific organic solvents unnecessary, because mu-EX would exploit a unique property of liquid water: the possibility of tuning its polarity to match the polarity of organic solvents appropriate for extraction of molecules of interest. The change of the permittivity of water would be achieved by exploiting interactions between the translational states of water molecules and an imposed electromagnetic field in the frequency range of 300 to 600 GHz. On a molecular level, these interactions would result in disruption of the three-dimensional hydrogen-bonding network among liquid-water molecules and subsequent solvation and hydrolysis of target molecules. The mu-EX is expected to be an efficient means of hydrolyzing chemical bonds in complex macromolecules as well and, thus, enabling analysis of the building blocks of these complex chemical systems. The mu-EX device would include a microfluidic channel, part of which would lie within a waveguide coupled to an electronically tuned source of broad-band electromagnetic radiation in the frequency range from 300 to 600 GHz (see figure). The part of the microfluidic channel lying in the waveguide would constitute an interaction volume. The dimensions of the interaction volume would be chosen in accordance with the anticipated amount of solid sample material needed to ensure extraction of sufficient amount of target molecules for detection and analysis. By means that were not specified at the time of reporting the information for this article, the solid sample material would be placed in the interaction volume. Then the electromagnetic field would be imposed within the waveguide and water would be pumped through the interaction volume to effect the extraction.

Extraction process optimization of polyphenols from Indian Citrus sinensis – as novel antiglycative agents in the management of diabetes mellitus

PubMed Central

2014-01-01

Background Diabetes mellitus is a chronic metabolic disorder characterized by increased blood glucose level. It has become an epidemic disease in the 21st century where, India leads the world with largest number of diabetic subjects. Non-enzymatic glycosylation (glycation) is severe form of diabetes, occurs between reducing sugar and proteins which results in the formation of advanced glycation end products (AGEs) that leads to the other complicated secondary disorders. In this context, Mangifera indica (Mango), Syzygium cumini (Jambul), Vitis vinifera (Grapes), Citrus sinensis (Orange), Artocarpus heterophyllus (Jackfruit), Manilkara zapota (Sapodilla) seeds were evaluated for their antiglyation activity. Attempts were made to isolate the polyphenols in the seeds that have recorded the maximum activity. Methods Different extraction methods (shake flask, centrifugation and pressurized hot water) using various extractants (organic solvents, hot water and pressurized hot water) were adopted to investigate the in vitro antiglycation activity. Central composite (CCD) design based Response Surface Methodology (RSM) was espoused to optimize the extraction process of polyphenols from the fruit seeds that have recorded poor antiglycation activity. The PTLC analysis was performed to isolate the polyphenols (Flavonoids and phenolic acids) and LC-PDA-MS analysis was done for structure prediction. Results Pressurized hot water extraction of Artocarpus heterophyllus (87.52%) and Citrus sinensis seeds (74.79%) was found to possess high and low antiglycation activity, respectively. The RSM mediated optimization process adopted for the Citrus sinensis seeds have revealed that 1:15 solvent ratio (hexane to heptane), 6 minutes and 1:20 solid to liquid ratio as the optimal conditions for the extraction of polyphenols with a maximum antiglycation activity (89.79%). The LC-PDA-MS analysis of preparative thin layer chromatography (PTLC) eluates of Artocarpus heterophyllus seed has showed the presence of compounds like quercetin (301.2), 4-hydroxy phenyl acetic acid (149.0), rhamnosyl-di-hexosyl quercetin sulphate (857.6), quercetin-3-O-xyloside (428.2), rutin (613.4), diosmetin (298.1) and luteolin (283.0). Conclusion The Artocarpus heterophyllus was observed to possess a significant antiglycation activity and the activity of Citrus sinensis was improved after the optimization process, which proved that both the seeds may be used as a traditional medicine in the management of chronic diabetes mellitus. PMID:24397983

Extraction process optimization of polyphenols from Indian Citrus sinensis - as novel antiglycative agents in the management of diabetes mellitus.

PubMed

Shakthi Deve, Asaithambi; Sathish Kumar, Thiyagarajan; Kumaresan, Kuppamuthu; Rapheal, Vinohar Stephen

2014-01-07

Diabetes mellitus is a chronic metabolic disorder characterized by increased blood glucose level. It has become an epidemic disease in the 21st century where, India leads the world with largest number of diabetic subjects. Non-enzymatic glycosylation (glycation) is severe form of diabetes, occurs between reducing sugar and proteins which results in the formation of advanced glycation end products (AGEs) that leads to the other complicated secondary disorders. In this context, Mangifera indica (Mango), Syzygium cumini (Jambul), Vitis vinifera (Grapes), Citrus sinensis (Orange), Artocarpus heterophyllus (Jackfruit), Manilkara zapota (Sapodilla) seeds were evaluated for their antiglyation activity. Attempts were made to isolate the polyphenols in the seeds that have recorded the maximum activity. Different extraction methods (shake flask, centrifugation and pressurized hot water) using various extractants (organic solvents, hot water and pressurized hot water) were adopted to investigate the in vitro antiglycation activity. Central composite (CCD) design based Response Surface Methodology (RSM) was espoused to optimize the extraction process of polyphenols from the fruit seeds that have recorded poor antiglycation activity. The PTLC analysis was performed to isolate the polyphenols (Flavonoids and phenolic acids) and LC-PDA-MS analysis was done for structure prediction. Pressurized hot water extraction of Artocarpus heterophyllus (87.52%) and Citrus sinensis seeds (74.79%) was found to possess high and low antiglycation activity, respectively. The RSM mediated optimization process adopted for the Citrus sinensis seeds have revealed that 1:15 solvent ratio (hexane to heptane), 6 minutes and 1:20 solid to liquid ratio as the optimal conditions for the extraction of polyphenols with a maximum antiglycation activity (89.79%). The LC-PDA-MS analysis of preparative thin layer chromatography (PTLC) eluates of Artocarpus heterophyllus seed has showed the presence of compounds like quercetin (301.2), 4-hydroxy phenyl acetic acid (149.0), rhamnosyl-di-hexosyl quercetin sulphate (857.6), quercetin-3-O-xyloside (428.2), rutin (613.4), diosmetin (298.1) and luteolin (283.0). The Artocarpus heterophyllus was observed to possess a significant antiglycation activity and the activity of Citrus sinensis was improved after the optimization process, which proved that both the seeds may be used as a traditional medicine in the management of chronic diabetes mellitus.

NON-BIOLOGICAL REACTIONS MAY BE AN IMPORTANT MECHANISM FOR NATURAL ATTENUATION OF CHLORINATED SOLVENTS

EPA Science Inventory

The role of non-biological transformation of chlorinated solvents was not considered in the U.S. EPA Technical Protocol for Evaluating Natural Attenuation of Chlorinated Solvents in Ground Water. This deficiency became very apparent when U.S. EPA conducted a beta test of the Pro...

Childhood Fish Consumption and Learning and Behavioral Disorders

PubMed Central

Carwile, Jenny L.; Butler, Lindsey J.; Janulewicz, Patricia A.; Winter, Michael R.; Aschengrau, Ann

2016-01-01

Fish is a major source of nutrients critical for brain development during early life. The importance of childhood fish consumption is supported by several studies reporting associations of n-3 polyunsaturated fatty acid (n-3 PUFA) supplementation with better behavior and school performance. However, fish may have a different effect than n-3 PUFA alone due to the neurotoxic effects of methylmercury, a frequent contaminant. We investigated associations of childhood fish consumption with learning and behavioral disorders in birth cohort study of the neurotoxic effects of early life exposure to solvent-contaminated drinking water. Childhood (age 7–12 years) fish consumption and learning and behavioral problems were reported in self-administered questionnaires (age 23–41 at questionnaire completion). Fish consumption was not meaningfully associated with repeating a grade, tutoring, attending summer school, special class placement, or low educational attainment. However, participants who ate fish several times a week had an elevated odds of Attention Deficit Disorder/Attention Deficit Hyperactivity Disorder (odds ratio: 5.2; 95% confidence interval: 1.5–18) compared to participants who did not eat fish. While these findings generally support the safety of the observed level of fish consumption, the absence of a beneficial effect may be attributed to insufficient fish intake or the choice of relatively low n-3 PUFA fish. PMID:27827868

Isomerization reaction dynamics and equilibrium at the liquid-vapor interface of water. A molecular-dynamics study

NASA Technical Reports Server (NTRS)

Benjamin, Ilan; Pohorille, Andrew

1993-01-01

The gauche-trans isomerization reaction of 1,2-dichloroethane at the liquid-vapor interface of water is studied using molecular-dynamics computer simulations. The solvent bulk and surface effects on the torsional potential of mean force and on barrier recrossing dynamics are computed. The isomerization reaction involves a large change in the electric dipole moment, and as a result the trans/gauche ratio is considerably affected by the transition from the bulk solvent to the surface. Reactive flux correlation function calculations of the reaction rate reveal that deviation from the transition-state theory due to barrier recrossing is greater at the surface than in the bulk water. This suggests that the system exhibits non-Rice-Ramsperger-Kassel-Marcus behavior due to the weak solvent-solute coupling at the water liquid-vapor interface.

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

PubMed Central

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

2017-01-01

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

Rational enhancement of enzyme performance in organic solvents. Final technical report, 1992--1996

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

Klibanov, A.M.

1996-12-31

This research focused on the following: the dependence of enzymatic activity of several model hydrolases in nonaqueous solvents; control of substrate selectivity of the protease subtilisin Carlsberg by the solvent; control of catalytic activity and enantioselectivity of this enzyme in organic solvents by immobilization support; lipase-catalyzed acylation of sugars in anhydrous hydrophobic media; the possibility of accelerating enzymatic processes in organic solvents by certain cosolvents; whether lipase catalysis in organic solvents can be enhanced by introducing interfaces in the in the reaction medium; the structure of proteins suspended in organic solvents; improving enzymatic enantioselectivity in organic solvents; analyzing the plungemore » in enzymatic activity upon replacing water with organic solvents; and the structural basis for the phenomenon of molecular memory of imprinted proteins in organic solvents.« less

Solvent dependence of the activation energy of attachment determined by single molecule observations of surfactant adsorption.

PubMed

Honciuc, Andrei; Baptiste, Denver Jn; Campbell, Ian P; Schwartz, Daniel K

2009-07-07

Single-molecule total internal reflection fluorescence microscopy was used to obtain real-time images of fluorescently labeled hexadecanoic (palmitic) acid molecules as they adsorbed at the interface between fused silica and three different solvents: hexadecane (HD), tetrahydrofuran (THF), and water. These solvents were chosen to explore the effect of solvent polarity on the activation energy associated with the attachment rate, i.e., the rate at which molecules were transferred to the surface from the near-surface layer. Direct counting of single-molecule events, made under steady-state conditions at extremely low coverage, provided direct, model-independent measurements of this attachment rate, in contrast with conventional ensemble-averaged methods, which are influenced by bulk transport and competing detachment processes. We found that the attachment rate increased with increasing temperature for all solvents. Arrhenius analyses gave activation energies of 5+/-2 kJ/mol for adsorption from HD, 10+/-2 kJ/mol for adsorption from THF, and 19+/-2 kJ/mol for adsorption from water. These energies increased systematically with the solvent polarity and, therefore, with the expected strength of the solvent-substrate interaction. We hypothesize that the adsorption of amphiphilic solute molecules from solution can be regarded as a competitive exchange between solute molecules and surface-bound solvent. In this scenario, adsorption is an activated process, and the activation energy for attachment is associated with the solvent-substrate interaction energy.

A molecular dynamics study of intramolecular proton transfer reaction of malonaldehyde in solution based upon a mixed quantum–classical approximation. II. Proton transfer reaction in non-polar solvent

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

Kojima, H.; Yamada, A.; Okazaki, S., E-mail: okazaki@apchem.nagoya-u.ac.jp

2015-05-07

The intramolecular proton transfer reaction of malonaldehyde in neon solvent has been investigated by mixed quantum–classical molecular dynamics (QCMD) calculations and fully classical molecular dynamics (FCMD) calculations. Comparing these calculated results with those for malonaldehyde in water reported in Part I [A. Yamada, H. Kojima, and S. Okazaki, J. Chem. Phys. 141, 084509 (2014)], the solvent dependence of the reaction rate, the reaction mechanism involved, and the quantum effect therein have been investigated. With FCMD, the reaction rate in weakly interacting neon is lower than that in strongly interacting water. However, with QCMD, the order of the reaction rates ismore » reversed. To investigate the mechanisms in detail, the reactions were categorized into three mechanisms: tunneling, thermal activation, and barrier vanishing. Then, the quantum and solvent effects were analyzed from the viewpoint of the reaction mechanism focusing on the shape of potential energy curve and its fluctuations. The higher reaction rate that was found for neon in QCMD compared with that found for water solvent arises from the tunneling reactions because of the nearly symmetric double-well shape of the potential curve in neon. The thermal activation and barrier vanishing reactions were also accelerated by the zero-point energy. The number of reactions based on these two mechanisms in water was greater than that in neon in both QCMD and FCMD because these reactions are dominated by the strength of solute–solvent interactions.« less

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

PubMed

Li, B O; Liu, Yuan

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

Re-construction layer effect of LiNi0.8Co0.15Mn0.05O2 with solvent evaporation process

NASA Astrophysics Data System (ADS)

Park, Kwangjin; Park, Jun-Ho; Hong, Suk-Gi; Choi, Byungjin; Heo, Sung; Seo, Seung-Woo; Min, Kyoungmin; Park, Jin-Hwan

2017-03-01

The solvent evaporation method on the structural changes and surface chemistry of the cathode and the effect of electrochemical performance of Li1.0Ni0.8Co0.15Mn0.05O2 (NCM) has been investigated. After dissolving of Li residuals using minimum content of solvent in order to minimize the damage of pristine material and the evaporation time, the solvent was evaporated without filtering and remaining powder was re-heated at 700 °C in oxygen environment. Two kinds of solvent, de-ionized water and diluted nitric acid, were used as a solvent. The almost 40% of Li residuals were removed using solvent evaporation method. The NCM sample after solvent evaporation process exhibited an increase in the initial capacity (214.3 mAh/g) compared to the pristine sample (207.4 mAh/g) at 0.1C because of enhancement of electric conductivity caused by decline of Li residuals. The capacity retention of NCM sample after solvent evaporation process (96.0% at the 50th cycle) was also improved compared to that of the pristine NCM sample (90.6% at the 50th cycle). The uniform Li residual layer after solvent treated and heat treatment acted like a coating layer, leading to enhance the cycle performance. The NCM sample using diluted nitric acid showed better performance than that using de-ionized water.

Process to prepare stable trifluorostyrene containing compounds grafted to base polymers using a solvent/water mixture

DOEpatents

Roelofs, Mark Gerrit; Yang, Zhen-Yu; Han, Amy Qi

2010-06-15

A fluorinated ion exchange polymer is prepared by grafting at least one grafting monomer derived from trifluorostyrene on to at least one base polymer in a organic solvent/water mixture. These ion exchange polymers are useful in preparing catalyst coated membranes and membrane electrode assemblies used in fuel cells.

Hazardous particle binder, coagulant and re-aerosolization inhibitor

DOEpatents

Krauter, Paula [Livermore, CA; Zalk, David [San Jose, CA; Hoffman, D Mark [Livermore, CA

2011-04-12

A copolymer and water/ethanol solvent solution capable of binding with airborne contaminants or potential airborne contaminants, such as biological weapon agents or toxic particulates, coagulating as the solvent evaporates, and adhering the contaminants to a surface so as to inhibit the re-suspension of such contaminants. The solution uses a water or ethanol/water mixture for the solvent, and a copolymer having one of several functional group sets so as to have physical and chemical characteristics of high adhesion, low viscosity, low surface tension, negative electrostatic charge, substantially neutral pH, and a low pKa. Use of the copolymer solution prevents re-aerosolization and transport of unwanted, reactive species thus increasing health and safety for personnel charged with decontamination of contaminated buildings and areas.

Hazardous particle binder, coagulant and re-aerosolization inhibitor

DOEpatents

Krauter, Paula; Zalk, David; Hoffman, D. Mark

2012-07-10

A copolymer and water/ethanol solvent solution capable of binding with airborne contaminants or potential airborne contaminants, such as biological weapon agents or toxic particulates, coagulating as the solvent evaporates, and adhering the contaminants to a surface so as to inhibit the re-suspension of such contaminants. The solution uses a water or ethanol/water mixture for the solvent, and a copolymer having one of several functional group sets so as to have physical and chemical characteristics of high adhesion, low viscosity, low surface tension, negative electrostatic charge, substantially neutral pH, and a low pKa. Use of the copolymer solution prevents re-aerosolization and transport of unwanted, reactive species thus increasing health and safety for personnel charged with decontamination of contaminated buildings and areas.

Improvement of bias-stability in amorphous-indium-gallium-zinc-oxide thin-film transistors by using solution-processed Y{sub 2}O{sub 3} passivation

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

An, Sungjin; Mativenga, Mallory; Kim, Youngoo

2014-08-04

We demonstrate back channel improvement of back-channel-etch amorphous-indium-gallium-zinc-oxide (a-IGZO) thin-film transistors by using solution-processed yttrium oxide (Y{sub 2}O{sub 3}) passivation. Two different solvents, which are acetonitrile (35%) + ethylene glycol (65%), solvent A and deionized water, solvent B are investigated for the spin-on process of the Y{sub 2}O{sub 3} passivation—performed after patterning source/drain (S/D) Mo electrodes by a conventional HNO{sub 3}-based wet-etch process. Both solvents yield devices with good performance but those passivated by using solvent B exhibit better light and bias stability. Presence of yttrium at the a-IGZO back interface, where it occupies metal vacancy sites, is confirmed by X-ray photoelectronmore » spectroscopy. The passivation effect of yttrium is more significant when solvent A is used because of the existence of more metal vacancies, given that the alcohol (65% ethylene glycol) in solvent A may dissolve the metal oxide (a-IGZO) through the formation of alkoxides and water.« less

Theoretical study on substituent and solvent effects for nanocubes formed with gear-shaped amphiphile molecules.

PubMed

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.

Focused microwave-assisted solvent extraction and HPLC determination of effective constituents in Eucommia ulmodies Oliv. (E. ulmodies).

PubMed

Li, Hui; Chen, Bo; Zhang, Zhaohui; Yao, Shouzhuo

2004-06-17

A new focused microwave-assisted solvent extraction method using water as solvent has been developed for leaching geniposidic and chlorogenic acids from Eucommia ulmodies Oliv. The extraction procedures were optimized using a two indexes orthogonal experimental design and graphical analysis, by varying irradiation time, solvent volume, solvent composition and microwave power. The optimum extraction conditions were obtained: for geniposidic acid, 50% micorwave power, 40s irradiation, and 80% (v/v) aqueous methanol as extraction solvent (20mlg(-1) sample); and for chlorogenic acid, 50% micorwave power, 30s irradiation, and 20% aqueous methanol (20mlg(-1) sample). The composition of the extraction solvent was optimized and can be directly used as the mobile phase in the HPLC separation. Quantification of organic acids was done by HPLC at room temperature using Spherigel C(18) chromatographic column (250 mm x4.6 mm , i.d. 5mum), the methanol:water:acetic acid (20:80:1.0, v/v) mobile phase and UV detection at 240nm. The R.S.D. of the extraction process for geniposidic and chlorogenic acid were 3.8 and 4.1%, respectively.

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

PubMed

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

2017-03-31

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

Molecular insights into early stage aggregation of di-Fmoc-L-lysine in binary mixture of organic solvent and water

NASA Astrophysics Data System (ADS)

Huda, Md Masrul; Rai, Neeraj

Molecular gels are relatively new class of soft materials, which are formed by the supramolecular aggregation of low molecular weight gelators (LMWGs) in organic solvents and/or water. Hierarchical self-assembly of small gelator molecules lead to three-dimensional complex fibrillar networks, which restricts the flow of solvents and results in viscous solid like materials or gels. These gels have drawn significant attentions for their potential applications for drug delivery, tissue engineering, materials for sensors etc. As of now, self-assembly of gelator molecules into one-dimensional fibers is not well understood, although that is very important to design new gelators for desired applications. Here, we present molecular dynamics study that provides molecular level insight into early stage aggregation of selected gelator, di-Fmoc-L-lysine in binary mixture of organic solvent and water. We will present the role of different functional groups of gelator molecule such as aromatic ring, amide, and carboxylic group on aggregation. We will also present the effect of concentrations of gelator and solvent on self-assembly of gelators. This study has captured helical fiber growth and branching of fiber, which is in good agreement with experimental observations.

Effect of various solvent on the specific amino acids of black soybean (Glycine soja) sprout

NASA Astrophysics Data System (ADS)

Kanetro, B.; Slamet, A.; Wazyka, A.

2018-01-01

The objective of this research was to study the effect of various solvent extractions on the specific amino acids as small peptide or free amino acids that was contained in the extract after removal of the macromolecule protein of black soybean sprouts. The experimental design of this research was randomized complete design with one factor, which was the three various solvent, i.e. hexane, ethanol and water. The black soybean seed was germinated for 36 h. The small peptide and free amino acids of black soybean sprout were isolated at 3 various of solvents extraction, and then the macromolecule proteins in the extracts were precipitated at the pH 4. The extracts of black soybean sprout after removal of the macromolecule protein were analysed by HPLC to determine the profile of amino acids for stimulation of insulin secretion. The result of this research showed that the extracts contained the small peptide and free amino acid for stimulation of insulin secretion. The best solvent extraction was water that was due to the content of Leu, Arg, Ala, Phe, Ile, and Lys of water extract was higher than hexane and ethanol extracts.

CHLORINATED SOLVENT PLUME CONTROL

EPA Science Inventory

This lecture will cover recent success in controlling and assessing the treatment of shallow ground water plumes of chlorinated solvents, other halogenated organic compounds, and methyl tert-butyl ether (MTBE).

40 CFR 60.601 - Definitions.

Code of Federal Regulations, 2014 CFR

2014-07-01

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

40 CFR 60.601 - Definitions.

Code of Federal Regulations, 2010 CFR

2010-07-01

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

40 CFR 60.601 - Definitions.

Code of Federal Regulations, 2013 CFR

2013-07-01

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

40 CFR 60.601 - Definitions.

Code of Federal Regulations, 2012 CFR

2012-07-01

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

40 CFR 60.601 - Definitions.

Code of Federal Regulations, 2011 CFR

2011-07-01

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

Influence of solvents in the preparation of cobalt sulfide for supercapacitors

NASA Astrophysics Data System (ADS)

Anil Kumar, Yedluri; Srinivasa Rao, S.; Punnoose, Dinah; Venkata Tulasivarma, Chebrolu; Gopi, Chandu V. V. M.; Prabakar, Kandasamy; Kim, Hee-Je

2017-09-01

In this study, cobalt sulfide (CoS) electrodes are synthesized using various solvents such as water, ethanol and a combination of the two via a facile chemical bath deposition method on Ni foam. The crystalline nature, chemical states and surface morphology of the prepared CoS nanoparticles are characterized using X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy and transition electron microscopy. The electrochemical properties of CoS electrodes are also evaluated using cyclic voltammetry, galvanostatic charge-discharge and electrochemical impedance spectroscopy. When used as an electrode for a supercapacitor, CoS prepared with ethanol as a solvent exhibits a capacitance of 41.36 F g-1 at 1.5 A g-1, which is significantly better than that prepared using water and water/ethanol-based solvents (31.66 and 18.94 F g-1 at 1.5 A g-1, respectively). This superior capacitance is attributed to the ideal surface morphology of the solvent, which allows for easy diffusion of electrolyte ions into the inner region of the electrode. High electrical conduction enables a high rate capability. These results suggest that CoS nanoparticles are highly promising for energy storage applications as well as photocatalysis, electrocatalysis, water splitting and solar cells, among others. These results show that CoS is a promising positive electrode material for practical supercapacitors.

Diffusion coefficients of nitric oxide in water: A molecular dynamics study

NASA Astrophysics Data System (ADS)

Pokharel, Sunil; Pantha, Nurapati; Adhikari, N. P.

2016-09-01

Self-diffusion coefficients along with the mutual diffusion coefficients of nitric oxide (NO) and SPC/E water (H2O) as solute and solvent of the mixture, have been studied within the framework of classical molecular dynamics level of calculations using GROMACS package. The radial distribution function (RDF) of the constituent compounds are calculated to study solute-solute, solute-solvent and solvent-solvent molecular interactions as a function of temperature. A dilute solution of five NO molecules (mole fraction 0.018) and 280 H2O molecules (mole fraction 0.982) has been taken as the sample. The self-diffusion coefficient of the solvent is calculated by using mean square displacement (MSD) where as that for solute (NO) is calculated by using MSD and velocity auto-correlation function (VACF). The results are then compared with the available experimental values. The results from the present work for water come in good agreement, very precise at low temperatures, with the experimental values. The diffusion coefficients of NO, on the other hands, agree well with the available theoretical studies, and also with experiment at low temperatures (up to 310 K). The results at the higher temperatures (up to 333 K), however, deviate significantly with the experimental observations. Also, the mutual diffusion coefficients of NO in water have been calculated by using Darken’s relation. The temperature dependence of the calculated diffusion coefficients follow the Arrhenius behavior.

Influence of solvents in the preparation of cobalt sulfide for supercapacitors

PubMed Central

Srinivasa Rao, S.; Punnoose, Dinah; Venkata Tulasivarma, Chebrolu; Gopi, Chandu V. V. M.; Prabakar, Kandasamy; Kim, Hee-Je

2017-01-01

In this study, cobalt sulfide (CoS) electrodes are synthesized using various solvents such as water, ethanol and a combination of the two via a facile chemical bath deposition method on Ni foam. The crystalline nature, chemical states and surface morphology of the prepared CoS nanoparticles are characterized using X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy and transition electron microscopy. The electrochemical properties of CoS electrodes are also evaluated using cyclic voltammetry, galvanostatic charge–discharge and electrochemical impedance spectroscopy. When used as an electrode for a supercapacitor, CoS prepared with ethanol as a solvent exhibits a capacitance of 41.36 F g−1 at 1.5 A g−1, which is significantly better than that prepared using water and water/ethanol-based solvents (31.66 and 18.94 F g−1 at 1.5 A g−1, respectively). This superior capacitance is attributed to the ideal surface morphology of the solvent, which allows for easy diffusion of electrolyte ions into the inner region of the electrode. High electrical conduction enables a high rate capability. These results suggest that CoS nanoparticles are highly promising for energy storage applications as well as photocatalysis, electrocatalysis, water splitting and solar cells, among others. These results show that CoS is a promising positive electrode material for practical supercapacitors. PMID:28989753

Assessment of central auditory processing in a group of workers exposed to solvents.

PubMed

Fuente, Adrian; McPherson, Bradley; Muñoz, Verónica; Pablo Espina, Juan

2006-12-01

Despite having normal hearing thresholds and speech recognition thresholds, results for central auditory tests were abnormal in a group of workers exposed to solvents. Workers exposed to solvents may have difficulties in everyday listening situations that are not related to a decrement in hearing thresholds. A central auditory processing disorder may underlie these difficulties. To study central auditory processing abilities in a group of workers occupationally exposed to a mix of organic solvents. Ten workers exposed to a mix of organic solvents and 10 matched non-exposed workers were studied. The test battery comprised pure-tone audiometry, tympanometry, acoustic reflex measurement, acoustic reflex decay, dichotic digit, pitch pattern sequence, masking level difference, filtered speech, random gap detection and hearing-in-noise tests. All the workers presented normal hearing thresholds and no signs of middle ear abnormalities. Workers exposed to solvents had lower results in comparison with the control group and previously reported normative data, in the majority of the tests.

Barium titanate tape properties for MLCC application using different binder systems

NASA Astrophysics Data System (ADS)

Yoon, Dang-Hyok

Most of multilayer ceramic capacitor (MLCC) industries are currently using solvent-based slip systems, although water-based slips have been receiving increasing attention due to reduced health and environmental hazards. The current work focuses on two main fields to meet the challenges in MLCC processing in aqueous media. One is the comparison between water- and solvent-based slip systems using design of experiments (DOE). The other is the understanding of Ba2+ ion leaching behavior in water and its effect on tape properties. For the first part, twenty four kinds of BaTiO3 slips were investigated using three different binder systems: one solvent-based, and two water-based systems. Tape casting, sintering and characterization were conducted. Slip viscosity and tape strength of the green tape depended significantly on the binder type. It was possible to achieve a higher green density for water-based system than that for a solvent-based one. Most of the green body properties from solvent-based system depended on the ceramic powder. On the other hand, the dispersant was the most significant factor for the green body properties of two water-based systems. Sintered properties such as microstructure and dielectric permittivity for three systems depended significantly on the type of ceramic powder. An optimization was performed for each system by means of a scorecard. By choosing the optimum condition, comparable results were drawn for the water-based system compared to a solvent-based one for MLCC application. For the second part, the amount of Ba2+ ion leaching from BaTiO3 in water was determined by an EDTA titration method. The greater extent and the faster rate of Ba2+ leaching were found at the lower solution pH. The excess free barium ions expressed by means of the Ba/Ti ratio adversely affected most tape properties. To passivate BaTiO 3 surface from Ba2+ ion leaching in water, passivation agent layer (PAL) was formed by drying the slurry after adding a commercial polymeric dispersant. Compared to the conventional dispersant adding method, this PAL method was more effective in reducing the amount of Ba2+ leaching. Moreover, using PAL did not deteriorate any of green and sintered properties of BaTiO3 tape.

Microcapsules fabricated from liquid marbles stabilized with latex particles.

PubMed

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.

Phenolic content and antioxidant activity of Hibiscus cannabinus L. seed extracts after sequential solvent extraction.

PubMed

Yusri, Noordin Mohd; Chan, Kim Wei; Iqbal, Shahid; Ismail, Maznah

2012-10-25

A sequential solvent extraction scheme was employed for the extraction of antioxidant compounds from kenaf (Hibiscus cannabinus L.) seeds. Yield of extracts varied widely among the solvents and was the highest for hexane extract (16.6% based on dry weight basis), while water extract exhibited the highest total phenolic content (18.78 mg GAE/g extract), total flavonoid content (2.49 mg RE/g extract), and antioxidant activities (p < 0.05). DPPH and hydroxyl radical scavenging, β-carotene bleaching, metal chelating activity, ferric thiocyanate and thiobarbituric acid reactive substances assays were employed to comprehensively assess the antioxidant potential of different solvent extracts prepared sequentially. Besides water, methanolic extract also exhibited high retardation towards the formation of hydroperoxides and thiobarbituric acid reactive substances in the total antioxidant activity tests (p < 0.05). As conclusion, water and methanol extracts of kenaf seed may potentially serve as new sources of antioxidants for food and nutraceutical applications.

The High-Resolution Structure of Activated Opsin Reveals a Conserved Solvent Network in the Transmembrane Region Essential for Activation.

PubMed

Blankenship, Elise; Vahedi-Faridi, Ardeschir; Lodowski, David T

2015-12-01

Rhodopsin, a light-activated G protein coupled receptor (GPCR), has been the subject of numerous biochemical and structural investigations, serving as a model receptor for GPCRs and their activation. We present the 2.3-Å resolution structure of native source rhodopsin stabilized in a conformation competent for G protein binding. An extensive water-mediated hydrogen bond network linking the chromophore binding site to the site of G protein binding is observed, providing connections to conserved motifs essential for GPCR activation. Comparison of this extensive solvent-mediated hydrogen-bonding network with the positions of ordered solvent in earlier crystallographic structures of rhodopsin photointermediates reveals both static structural and dynamic functional water-protein interactions present during the activation process. When considered along with observations that solvent occupies similar positions in the structures of other GPCRs, these analyses strongly support an integral role for this dynamic ordered water network in both rhodopsin and GPCR activation. Copyright © 2015 Elsevier Ltd. All rights reserved.

Ultra-lightweight and highly porous carbon aerogels from bamboo pulp fibers as an effective sorbent for water treatment

NASA Astrophysics Data System (ADS)

Yuan, Wei; Zhang, Xiaofang; Zhao, Jiangqi; Li, Qingye; Ao, Chenghong; Xia, Tian; Zhang, Wei; Lu, Canhui

Sorbents derived from biomass provide a novel approach to settle issues of organic solvent and/or oil leakage. In this work, a novel carbon aerogel (CA) was prepared as sorbents using the cheap and abundant bamboo pulp fibers as precursors through the pyrolysis method. The CA displayed an ultra-low density (5.65 mg cm-3), high hydrophobicity (water contact angle of 135.9°) and a large specific surface area (379.39 m2 g-1) as well as great mechanical properties. The absorption capacities of CA for organic solvents/oils were extraordinary (50-150 g/g). Particularly, its absorption on organic solvents was superior to many other bio-based CAs. The reusability of CA was also found impressive. For over five absorption-desorption cycles, the CA still showed excellent absorption behaviors on organic solvents and oils. Importantly, the fabrication process of CA is quite simple and environmentally friendly, demonstrating high potentials for future water treatment applications.

Hybrid MC/QC simulations of water-assisted proton transfer in nucleosides. Guanosine and its analog acyclovir.

PubMed

Markova, Nadezhda; Pejov, Ljupco; Stoyanova, Nina; Enchev, Venelin

2017-05-01

To provide an in-depth insight into the molecular basis of spontaneous tautomerism in DNA and RNA base pairs, a hybrid Monte Carlo (MC)-quantum chemical (QC) methodology is implemented to map two-dimensional potential energy surfaces along the reaction coordinates of solvent-assisted proton transfer processes in guanosine and its analog acyclovir in aqueous solution. The solvent effects were simulated by explicit inclusion of water molecules that model the relevant part of the first hydration shell around the solute. The position of these water molecules was estimated by carrying out a classical Metropolis Monte Carlo simulation of dilute water solutions of the guanosine (Gs) and acyclovir (ACV) and subsequently analyzing solute-solvent intermolecular interactions in the statistically-independent MC-generated configurations. The solvent-assisted proton transfer processes were further investigated using two different ab initio MP2 quantum chemical approaches. In the first one, potential energy surfaces of the 'bare' finite solute-solvent clusters containing Gs/ACV and four water molecules (MP2/6-31+G(d,p) level) were explored, while within the second approach, these clusters were embedded in 'bulk' solvent treated as polarizable continuum (C-PCM/MP2/6-31+G(d,p) level of theory). It was found that in the gas phase and in water solution, the most stable tautomer for guanosine and acyclovir is the 1H-2-amino-6-oxo form followed by the 2-amino-6-(sZ)-hydroxy form. The energy barriers of the water-assisted proton transfer reaction in guanosine and in acyclovir are found to be very similar - 11.74 kcal mol -1 for guanosine and 11.16 kcal mol -1 for acyclovir, and the respective rate constants (k = 1.5 × 10 1 s -1 , guanosine and k = 4.09 × 10 1 s -1 , acyclovir), are sufficiently large to generate the 2-amino-6-(sZ)-hydroxy tautomer. The analysis of the reaction profiles in both compounds shows that the proton transfer processes occur through the asynchronous concerted mechanism.

Effects of solvent concentration and composition on protein dynamics: 13C MAS NMR studies of elastin in glycerol-water mixtures.

PubMed

Demuth, Dominik; Haase, Nils; Malzacher, Daniel; Vogel, Michael

2015-08-01

We use (13)C CP MAS NMR to investigate the dependence of elastin dynamics on the concentration and composition of the solvent at various temperatures. For elastin in pure glycerol, line-shape analysis shows that larger-scale fluctuations of the protein backbone require a minimum glycerol concentration of ~0.6 g/g at ambient temperature, while smaller-scale fluctuations are activated at lower solvation levels of ~0.2 g/g. Immersing elastin in various glycerol-water mixtures, we observe at room temperature that the protein mobility is higher for lower glycerol fractions in the solvent and, thus, lower solvent viscosity. When decreasing the temperature, the elastin spectra approach the line shape for the rigid protein at 245 K for all studied samples, indicating that the protein ceases to be mobile on the experimental time scale of ~10(-5) s. Our findings yield evidence for a strong coupling between elastin fluctuations and solvent dynamics and, hence, such interaction is not restricted to the case of protein-water mixtures. Spectral resolution of different carbon species reveals that the protein-solvent couplings can, however, be different for side chain and backbone units. We discuss these results against the background of the slaving model for protein dynamics. Copyright © 2015 Elsevier B.V. All rights reserved.

Temperature-dependent phase behaviour of tetrahydrofuran–water alters solubilization of xylan to improve co-production of furfurals from lignocellulosic biomass

DOE PAGES

Smith, Micholas Dean; Cai, Charles M.; Cheng, Xiaolin; ...

2018-03-06

Xylose, Xylan, Hemicellulose, CELF, THF, Co-solvent, Pretreatment, Biomass ABSTRACT: Xylan is an important polysaccharide found in the hemicellulose fraction of lignocellulosic biomass that can be hydrolysed to xylose and further dehydrated to the furfural, an important renewable platform fuel precursor. Here, pairing molecular simulation and experimental evidences, we reveal how the unique temperature-dependent phase behaviour of water-tetrahydrofuran (THF) co-solvent can delay xylan solubilization to synergistically improve catalytic co-processing of biomass to furfural and 5-HMF. Our results indicate, based on polymer correlations between polymer conformational behaviour and solvent quality, that both co-solvent and aqueous environments serve as ‘good’ solvents for xylan.more » Interestingly, the simulations also revealed that unlike other cell-wall components (i.e., lignin and cellulose), the make-up of the solvation shell of xylan in THF-water is dependent on the temperature-phase behaviour. At temperatures between 333K and 418K, THF and water become immiscible, and THF is evacuated from the solvation shell of xylan, while above and below this temperature range, THF and water are both present in the polysaccharide’s solvation shell. This suggested that the solubilization of xylan in THF-water may be similar to aqueous-only solutions at temperatures between 333K and 418K and different outside this range. Experimental reactions on beachwood xylan corroborate this hypothesis by demonstrating 2-fold reduction of xylan solubilization in THF-water within a miscible temperature regime (445K) and unchanged solubilization within an immiscible regime (400K). Translating this phase-dependent behaviour to processing of maple wood chips, we demonstrate how the weaker xylan solvation in THF-water under miscible conditions can delay furfural production from xylose, allowing 5-HMF production from cellulose to “catch-up” such that their high yield production from biomass can be synergized in a single pot reaction.« less

Impact of Water-Dilution on the Solvation Properties of the Ionic Liquid 1-Methyltriethoxy-3-ethylimidazolium Acetate for Model Biomass Molecules.

PubMed

Schutt, Timothy C; Hegde, Govind A; Bharadwaj, Vivek S; Johns, Adam J; Maupin, C Mark

2017-02-02

Many studies have suggested that the processing of lignocellulosic biomass could provide a renewable feedstock to supplant much of the current demand on petroleum sources. Currently, alkyl imidazolium-based ionic liquids (ILs) have shown considerable promise in the pretreatment, solvation, and hydrolysis of lignocellulosic materials although their high cost and unfavorable viscosity has limited their widespread use. Functionalizing these ILs with an oligo(ethoxy) tail has previously been shown through experiment to decrease the IL's viscosity resulting in enhanced mass transport characteristics, in addition to other favorable traits including decreased inhibition of some enzymes. Additionally, the use of cosolvents to mitigate the cost and unfavorable traits of ILs is an area of growing interest with particular attention on water as the presence of water in biomass processes is inevitable. Through the use of biased and unbiased molecular dynamics (MD) simulations, this study provides a molecular-level perspective of the various solvent-solvent and solvent-solute interactions in binary mixtures of water and 1-methyltriethoxy-3-ethylimidazolium acetate ([Me-(OEt) 3 -Et-IM + ] [OAc - ]) in the presence of model cellulose compounds (i.e., glucose and cellobiose). It is observed that at ∼75% w/w IL and water a transition in the nanostructure of the solvent occurs between water-like and IL-like solvation characteristics. It is shown that H-bonding interactions between the anion and water are a major driving force that significantly impacts the solvent properties of the IL as well as conformational preferences of the cellulosic model compound. In addition, it is found that the oligo(ethoxy) cation tail is responsible for the reduction in the propensity for tail aggregation as compared to alkyl tails of similar length, which, combined with increased ionic shielding, results in increased diffusion and enhanced water-like solvation characteristics.

Temperature-dependent phase behaviour of tetrahydrofuran–water alters solubilization of xylan to improve co-production of furfurals from lignocellulosic biomass

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

Smith, Micholas Dean; Cai, Charles M.; Cheng, Xiaolin

Xylose, Xylan, Hemicellulose, CELF, THF, Co-solvent, Pretreatment, Biomass ABSTRACT: Xylan is an important polysaccharide found in the hemicellulose fraction of lignocellulosic biomass that can be hydrolysed to xylose and further dehydrated to the furfural, an important renewable platform fuel precursor. Here, pairing molecular simulation and experimental evidences, we reveal how the unique temperature-dependent phase behaviour of water-tetrahydrofuran (THF) co-solvent can delay xylan solubilization to synergistically improve catalytic co-processing of biomass to furfural and 5-HMF. Our results indicate, based on polymer correlations between polymer conformational behaviour and solvent quality, that both co-solvent and aqueous environments serve as ‘good’ solvents for xylan.more » Interestingly, the simulations also revealed that unlike other cell-wall components (i.e., lignin and cellulose), the make-up of the solvation shell of xylan in THF-water is dependent on the temperature-phase behaviour. At temperatures between 333K and 418K, THF and water become immiscible, and THF is evacuated from the solvation shell of xylan, while above and below this temperature range, THF and water are both present in the polysaccharide’s solvation shell. This suggested that the solubilization of xylan in THF-water may be similar to aqueous-only solutions at temperatures between 333K and 418K and different outside this range. Experimental reactions on beachwood xylan corroborate this hypothesis by demonstrating 2-fold reduction of xylan solubilization in THF-water within a miscible temperature regime (445K) and unchanged solubilization within an immiscible regime (400K). Translating this phase-dependent behaviour to processing of maple wood chips, we demonstrate how the weaker xylan solvation in THF-water under miscible conditions can delay furfural production from xylose, allowing 5-HMF production from cellulose to “catch-up” such that their high yield production from biomass can be synergized in a single pot reaction.« less

Effect of ethanol as a co-solvent on the aerosol performance and stability of spray-dried lysozyme.

PubMed

Ji, Shuying; Thulstrup, Peter Waaben; Mu, Huiling; Hansen, Steen Honoré; van de Weert, Marco; Rantanen, Jukka; Yang, Mingshi

2016-11-20

In the spray drying process, organic solvents can be added to facilitate drying, accommodate certain functional excipients, and modify the final particle characteristics. In this study, lysozyme was used as a model pharmaceutical protein to study the effect of ethanol as a co-solvent on the stability and aerosol performance of spray-dried protein. Lysozyme was dissolved in solutions with various ratios of ethanol and water, and subsequently spray-dried. A change from spherical particles into wrinkled and folded particles was observed upon increasing the ratio of ethanol in the feed. The aerosol performance of the spray-dried lysozyme from ethanol-water solution was improved compared to that from pure water. The conformation of lysozyme in the ethanol-water solution and spray dried powder was altered, but the native structure of lysozyme was restored upon reconstitution in water after the spray drying process. The enzymatic activities of the spray-dried lysozyme showed no significant impact of ethanol; however, the lysozyme enzymatic activity was ca. 25% lower compared to the starting material. In conclusion, the addition of ethanol as a co-solvent in the spray drying feed for lysozyme did not compromise the conformation of the protein after drying, while it improved the inhaled aerosol performance. Copyright © 2016 Elsevier B.V. All rights reserved.

Platinum nanoparticles on carbon-nanotube support prepared by room-temperature reduction with H2 in ethylene glycol/water mixed solvent as catalysts for polymer electrolyte membrane fuel cells

NASA Astrophysics Data System (ADS)

Zheng, Yuying; Dou, Zhengjie; Fang, Yanxiong; Li, Muwu; Wu, Xin; Zeng, Jianhuang; Hou, Zhaohui; Liao, Shijun

2016-02-01

Polyol approach is commonly used in synthesizing Pt nanoparticles in polymer electrolyte membrane fuel cells. However, the application of this process consumes a great deal of time and energy, as the reduction of precursors requires elevated temperatures and several hours. Moreover, the ethylene glycol and its oxidizing products bound to Pt are difficult to remove. In this work, we utilize the advantages of ethylene glycol and prepare Pt nanoparticles through a room-temperature hydrogen gas reduction in an ethylene glycol/water mixed solvent, which is followed by subsequent harvesting by carbon nanotubes as electrocatalysts. This method is simple, facile, and time-efficient, as the entire room-temperature reduction process is completed in a few minutes. As the solvent changes from water to an ethylene glycol/water mix, the size of Pt nanoparticles varies from 10 to 3 nm and their shape transitions from polyhedral to spherical. Pt nanoparticles prepared in a 1:1 volume ratio mixture of ethylene glycol/water are uniformly dispersed with an average size of ∼3 nm. The optimized carbon nanotube-supported Pt electrocatalyst exhibits excellent methanol oxidation and oxygen reduction activities. This work demonstrates the potential use of mixed solvents as an approach in materials synthesis.

Deep eutectic solvents as efficient solvent system for the extraction of κ-carrageenan from Kappaphycus alvarezii.

PubMed

Das, Arun Kumar; Sharma, Mukesh; Mondal, Dibyendu; Prasad, Kamalesh

2016-01-20

Three different deep eutectic solvents (DESs) prepared by the complexation of choline chloride with urea, ethylene glycol and glycerol along with their hydrated counterparts were used for the selective extraction of κ-carrageenan from Kappaphycus alvarezii. Upon comparison of the quality of the polysaccharide with the one obtained using water as extraction media as well as the one extracted using widely practiced conventional method, it was found that, the physicochemical as well as rheological properties of κ-carrageenan obtained using DESs as solvents was at par to the one obtained using conventional method and was superior in quality when compared to κ-carrageenan obtained using water as solvent. Considering the tedious nature of the extraction method employed in conventional extraction process, the DESs can be considered as suitable alternative solvents for the facile extraction of the polysaccharide directly from the seaweed. However, among the hydrated and non-hydrated DESs, the hydrated ones were found to be more effective in comparison to their non-hydrated counterparts. Copyright © 2015 Elsevier Ltd. All rights reserved.

Evaluation of Production Version of the NASA Improved Inorganic-Organic Separator

NASA Technical Reports Server (NTRS)

Sheibley, D.

1983-01-01

The technology of an inorganic-organic (I/O) separator, which demonstrated improved flexibility, reduced cost, production feasibility and improved cycle life was developed. Substrates to replace asbestos and waterbased separator coatings to replace the solvent based coatings were investigated. An improved fuel cell grade asbestos sheet was developed and a large scale production capability for the solvent based I/O separator was demonstrated. A cellulose based substrate and a nonwoven polypropylene fiber substrate were evaluated as replacements for the asbestos. Both the cellulose and polypropylene substrates were coated with solvent based and water based coatings to produce a modified I/O separator. The solvent based coatings were modified to produce aqueous separator coatings with acceptable separator properties. A single ply fuel cell grade asbestos with a binder (BTA) was produced. It has shown to be an acceptable substrate for the solvent and water based separator coatings, an acceptable absorber for alkaline cells, and an acceptable matrix for alkaline fuel cells. The original solvent based separator (K19W1), using asbestos as a substrate, was prepared.

Comparison of Dimethyl Sulfoxide and Water as Solvents for Echinocandin Susceptibility Testing by the EUCAST Methodology

PubMed Central

Alastruey-Izquierdo, Ana; Gómez-López, Alicia; Arendrup, Maiken C.; Lass-Florl, Cornelia; Hope, William W.; Perlin, David S.; Rodriguez-Tudela, Juan L.

2012-01-01

Ninety-six strains of Candida, including 29 resistant and 67 susceptible isolates with mutations in the FKS1 and FKS2 genes were tested by the European Committee on Antibiotic Susceptibility Testing EDef 7.1 and 7.2 methodologies to determine the impact on the MIC when water was replaced with dimethyl sulfoxide (DMSO) as the solvent for caspofungin and micafungin. The MICs were significantly lower and the MIC ranges were narrower when DMSO was used as the solvent. The use of DMSO may help to better discriminate between susceptible and resistant populations. PMID:22535988

Comparison of dimethyl sulfoxide and water as solvents for echinocandin susceptibility testing by the EUCAST methodology.

PubMed

Alastruey-Izquierdo, Ana; Gómez-López, Alicia; Arendrup, Maiken C; Lass-Florl, Cornelia; Hope, William W; Perlin, David S; Rodriguez-Tudela, Juan L; Cuenca-Estrella, Manuel

2012-07-01

Ninety-six strains of Candida, including 29 resistant and 67 susceptible isolates with mutations in the FKS1 and FKS2 genes were tested by the European Committee on Antibiotic Susceptibility Testing EDef 7.1 and 7.2 methodologies to determine the impact on the MIC when water was replaced with dimethyl sulfoxide (DMSO) as the solvent for caspofungin and micafungin. The MICs were significantly lower and the MIC ranges were narrower when DMSO was used as the solvent. The use of DMSO may help to better discriminate between susceptible and resistant populations.

Membrane formation in liquids by adding an antagonistic salt

NASA Astrophysics Data System (ADS)

Sadakane, Koichiro; Seto, Hideki

2018-03-01

Antagonistic salts are composed of hydrophilic and hydrophobic ions. In a binary mixture, such as water and organic solvent, these ion pairs preferentially dissolve to those phases, respectively, and there is a coupling between the charge density and the composition. The heterogeneous distribution of ions forms a large electric double layer at the interface between these solvents. This reduces the interfacial tension between water and organic solvent, and stabilizes an ordered structure, such as a membrane. These phenomena have been extensively studied from both theoretical and experimental point of view. In addition, the numerical simulations can reproduce such ordered structures.

Spectroscopic properties of vitamin E models in solution

NASA Astrophysics Data System (ADS)

Oliveira, L. B. A.; Colherinhas, G.; Fonseca, T. L.; Castro, M. A.

2015-05-01

We investigate the first absorption band and the 13C and 17O magnetic shieldings of vitamin E models in chloroform and in water using the S-MC/QM methodology in combination with the TD-DFT and GIAO approaches. The results show that the solvent effects on these spectroscopic properties are small but a proper description of the solvent shift for 17O magnetic shielding of the hydroxyl group in water requires the use of explicit solute-solvent hydrogen bonds. In addition, the effect of the replacement of hydrogen atoms by methyl groups in the vitamin E models only affects magnetic shieldings.

Interfacial solvation thermodynamics

NASA Astrophysics Data System (ADS)

Ben-Amotz, Dor

2016-10-01

Previous studies have reached conflicting conclusions regarding the interplay of cavity formation, polarizability, desolvation, and surface capillary waves in driving the interfacial adsorptions of ions and molecules at air-water interfaces. Here we revisit these questions by combining exact potential distribution results with linear response theory and other physically motivated approximations. The results highlight both exact and approximate compensation relations pertaining to direct (solute-solvent) and indirect (solvent-solvent) contributions to adsorption thermodynamics, of relevance to solvation at air-water interfaces, as well as a broader class of processes linked to the mean force potential between ions, molecules, nanoparticles, proteins, and biological assemblies.

Water as a matrix for life

NASA Technical Reports Server (NTRS)

Pohorille, Andrew

2005-01-01

Life is based on non-covalent interactions. They might be either specific (enzyme-substrate interactions, selective ion transport) or nonspecific (lipid-lipid and lipid-protein interactions needed for membrane integrity, fusion and division). Their strength needs to be properly tuned, and this is mediated by the solvent. If interactions are too weak, there might be undesired response to natural fluctuations of physical and chemical parameters. If they are too strong it could impede kinetics and energetics of cellular processes. Thus, the solvent must allow for balancing these interactions. Physical and chemical properties of solvent provide strong constraints for life. Water exhibits a remarkable trait that it promotes both solvophobic and solvophilic interactions. Solvophobic interactions; related to high dielectric constant of the solvent) are necessary for self-organization of matter whereas solvophilic interactions are needed to ensure solubility of polar species. Water offers a large temperature domain of stable liquid and the characteristics hydrophobic effects are a consequence of the temperature in sensitivity of essential properties of its liquid state. Water, however, is not the only liquid with these favorable properties. I will compare in detail properties of water and other pure liquids or their mixtures that have a high dielectric constant and simultaneously support self-organization. I will also discuss properties of water that are unfavorable to life (e.g. its chemical activity against polymerization reactions) and close with summarizing what are alternatives to water as a matrix of life in space.

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.

Influence of the composition of aqueous dimethylsulfoxide solvent on thermodynamics of complexing between 18-crown-6-ether and D,L-alanine

NASA Astrophysics Data System (ADS)

Usacheva, T. R.; Kuzmina, I. A.; Sharnin, V. A.; Chernov, I. V.; Matteoli, E.

2012-07-01

Standard thermodynamic parameters (log K o, Δr H o, TΔr S o) of complexing 18-crown-6 ether (18C6) with D,L-alanine (Ala) in mixed water-dimethysulfoxide (H2O-DMSO) solvents are calculated on the basis of calorimetric titration results. A rise in the DMSO concentration in mixed solvent is found to increase stability and increase the exothermicity of the formation of [Ala-18C6] molecular complex. Changes in the reaction energetic are shown to be determined by changes in the solvation state of 18C6 that is the characteristic of the reactions of molecular complex formation between 18C6 and D,L-alanine or glycine in water-organic solvents.

Contribution of Hydrogen Bonds to Paper Strength Properties.

PubMed

Przybysz, Piotr; Dubowik, Marcin; Kucner, Marta Anna; Przybysz, Kazimierz; Przybysz Buzała, Kamila

2016-01-01

The objective of this work was to investigate the influence of hydrogen bonds between fibres on static and dynamic strength properties of paper. A commercial bleached pinewood kraft pulp was soaked in water, refined in a PFI, and used to form paper webs in different solvents, such as water, methanol, ethanol, n-propanol and n-butanol, to determine the effect of their dipole moment on static and dynamic strength properties of resulting paper sheets. Paper which was formed in water, being the solvent of the highest dipole moment among the tested ones, showed the highest breaking length and tear resistance. When paper webs were formed in n-butanol, which was the least polar among the solvents, these parameters were reduced by around 75%. These results provide evidence of the importance of water in paper web formation and strong impact of hydrogen bonds between fibres on strength properties of paper.

Contribution of Hydrogen Bonds to Paper Strength Properties

PubMed Central

Przybysz, Piotr; Dubowik, Marcin; Kucner, Marta Anna; Przybysz, Kazimierz; Przybysz Buzała, Kamila

2016-01-01

The objective of this work was to investigate the influence of hydrogen bonds between fibres on static and dynamic strength properties of paper. A commercial bleached pinewood kraft pulp was soaked in water, refined in a PFI, and used to form paper webs in different solvents, such as water, methanol, ethanol, n-propanol and n-butanol, to determine the effect of their dipole moment on static and dynamic strength properties of resulting paper sheets. Paper which was formed in water, being the solvent of the highest dipole moment among the tested ones, showed the highest breaking length and tear resistance. When paper webs were formed in n-butanol, which was the least polar among the solvents, these parameters were reduced by around 75%. These results provide evidence of the importance of water in paper web formation and strong impact of hydrogen bonds between fibres on strength properties of paper. PMID:27228172

Solubility of Naproxen in Polyethylene Glycol 200 + Water Mixtures at Various Temperatures

PubMed Central

Panahi-Azar, Vahid; Soltanpour, Shahla; Martinez, Fleming; Jouyban, Abolghasem

2015-01-01

The solubility of naproxen in binary mixtures of polyethylene glycol 200 (PEG 200) + water at the temperature range from 298.0 K to 318.0 K were reported. The combinations of Jouyban-Acree model + van’t Hoff and Jouyban-Acree model + partial solubility parameters were used to predict the solubility of naproxen in PEG 200 + water mixtures at different temperatures. Combination of Jouyban-Acree model with van’t Hoff equation can be used to predict solubility in PEG 200 + water with only four solubility data in mono-solvents. The obtained solubility calculation errors vary from ~ 17 % up to 35 % depend on the number of required input data. Non-linear enthalpy-entropy compensation was found for naproxen in the investigated solvent system and the Jouyban−Acree model provides reasonably accurate mathematical descriptions of the thermodynamic data of naproxen in the investigated binary solvent systems. PMID:26664370

Optimization of extraction conditions of some polyphenolic compounds from parsley leaves (Petroselinum crispum).

PubMed

Kuźma, Paula; Drużyńska, Beata; Obiedziński, Mieczysław

2014-01-01

Parsley leaf is a rich source of natural antioxidants, which serve a lot of functions in human body and prevent food from oxidation processes. The aim of the study was to investigate the influence of different extraction solvents and times of extraction on natural antioxidants content. Owing to the knowledge of the properties of extracted components and solvents, as well as their interactions, it is possible to achieve a high effectiveness of active compounds recovery. Three different extraction solvents (acetone 70% in water, methanol 80% in water and distilled water) and different times of extraction (30 and 60 minutes) were used to determine the efficiency of extraction of polyphenols and catechins, antioxidant activity against free radicals DPPH and ABTS and the ability to chelate ion Fe(2+) in dried parsley leaves. Other natural antioxidants contents in parsley leaves were also determined. In this study the best extraction solvent for polyphenols was acetone 70% and for catechins was distilled water. All extracts examined displayed the antioxidative activity, but water was the best solvent in the method of assaying the activity against ABTS(•+) and Fe(2+) ions chelating capability, whereas methanol turned out to be the least effective in this respect. Opposite results were observed in the case of determining the activity against DPPH(•). The prolongation of the extraction time enhanced or decreased antiradical activity in some cases. Additionally, important biologically active compounds in parsley leaves, such as vitamin C (248.31 mg/100 g dry matter), carotenoids (31.28 mg/100 g dry matter), chlorophyll (0.185 mg/g dry matter) were also analysed.

Multi-residue method for determination of 58 pesticides, pharmaceuticals and personal care products in water using solvent demulsification dispersive liquid-liquid microextraction combined with liquid chromatography-tandem mass spectrometry.

PubMed

Caldas, Sergiane Souza; Rombaldi, Caroline; Arias, Jean Lucas de Oliveira; Marube, Liziane Cardoso; Primel, Ednei Gilberto

2016-01-01

A rapid and efficient sample pretreatment using solvent-based de-emulsification dispersive liquid-liquid microextraction (SD-DLLME) coupled with liquid chromatography-tandem mass spectrometry (LC-MS/MS) was studied for the extraction of 58 pharmaceuticals and personal care products (PPCPs) and pesticides from water samples. Type and volume of extraction and disperser solvents, pH, salt addition, amount of salt and type of demulsification solvent were evaluated. Limits of quantification (LOQ) in the range from 0.0125 to 1.25 µg L(-1) were reached, and linearity was in the range from the LOQ of each compound to 25 μg L(-1). Recoveries ranged from 60% to 120% for 84% of the compounds, with relative standard deviations lower than 29%. The proposed method demonstrated, for the first time, that sample preparation by SD-DLLME with determination by LC-MS/MS can be successfully used for the simultaneous extraction of 32 pesticides and 26 PPCPs from water samples. The entire procedure, including the extraction of 58 organic compounds from the aqueous sample solution and the breaking up of the emulsion after extraction with water, rather than with an organic solvent, was environmentally friendly. In addition, this technique was less expensive and faster than traditional techniques. Finally, the analytical method under study was successfully applied to the analysis of all 58 pesticides and PPCPs in surface water samples. Copyright © 2015 Elsevier B.V. All rights reserved.

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.

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

PubMed

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

2008-02-15

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

Solvophobic and solvophilic contributions in the water-to-aqueous guanidinium chloride transfer free energy of model peptides

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.

Solvophobic and solvophilic contributions in the water-to-aqueous guanidinium chloride transfer free energy of model peptides.

PubMed

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.

High mobility organic field-effect transistor based on water-soluble deoxyribonucleic acid via spray coating

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

Shi, Wei; Han, Shijiao; Huang, Wei

High mobility organic field-effect transistors (OFETs) by inserting water-soluble deoxyribonucleic acid (DNA) buffer layer between electrodes and pentacene film through spray coating process were fabricated. Compared with the OFETs incorporated with DNA in the conventional organic solvents of ethanol and methanol: water mixture, the water-soluble DNA based OFET exhibited an over four folds enhancement of field-effect mobility from 0.035 to 0.153 cm{sup 2}/Vs. By characterizing the surface morphology and the crystalline structure of pentacene active layer through atomic force microscope and X-ray diffraction, it was found that the adoption of water solvent in DNA solution, which played a key role inmore » enhancing the field-effect mobility, was ascribed to both the elimination of the irreversible organic solvent-induced bulk-like phase transition of pentacene film and the diminution of a majority of charge trapping at interfaces in OFETs.« less

Morphological Evolution of Gyroid-Forming Block Copolymer Thin Films with Varying Solvent Evaporation Rate.

PubMed

Wu, Yi-Hsiu; Lo, Ting-Ya; She, Ming-Shiuan; Ho, Rong-Ming

2015-08-05

In this study, we aim to examine the morphological evolution of block copolymer (BCP) nanostructured thin films through solvent evaporation at different rates for solvent swollen polystyrene-block-poly(l-lactide) (PS-PLLA). Interesting phase transitions from disorder to perpendicular cylinder and then gyroid can be found while using a partially selective solvent for PS to swell PS-PLLA thin film followed by solvent evaporation. During the transitions, gyroid-forming BCP thin film with characteristic crystallographic planes of (111)G, (110)G, and (211)G parallel to air surface can be observed, and will gradually transform into coexisting (110)G and (211)G planes, and finally transforms to (211)G plane due to the preferential segregation of constituted block to the surface (i.e., the thermodynamic origin for self-assembly) that affects the relative amount of each component at the air surface. With the decrease on the evaporation rate, the disorder phase will transform to parallel cylinder and then directly to (211)G without transition to perpendicular cylinder phase. Most importantly, the morphological evolution of PS-PLLA thin films is strongly dependent upon the solvent removal rate only in the initial stage of the evaporation process due to the anisotropy of cylinder structure. Once the morphology is transformed back to the isotropic gyroid structure after long evaporation, the morphological evolution will only relate to the variation of the surface composition. Similar phase transitions at the substrate can also be obtained by controlling the ratio of PLLA-OH to PS-OH homopolymers to functionalize the substrate. As a result, the fabrication of well-defined nanostructured thin films with controlled orientation can be achieved by simple swelling and deswelling with controlled evaporation rate.

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

PubMed

Wang, Zhi-Xiang; Duan, Yong

2004-11-15

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

The effects of esterified solvents on the diffusion of a model compound across human skin: an ATR-FTIR spectroscopic study.

PubMed

McAuley, W J; Chavda-Sitaram, S; Mader, K T; Tetteh, J; Lane, M E; Hadgraft, J

2013-04-15

Attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy has been used to investigate the effects of three fatty acid esters on skin permeation. Propylene glycol diperlargonate (DPPG), isopropyl myristate (IPM) and isostearyl isostearate (ISIS) were selected as pharmaceutically relevant solvents with a range of lipophilicities and cyanophenol (CNP) was used as a model drug. The resultant data were compared with that obtained when water was used as the solvent. The diffusion of CNP, DPPG and IPM across epidermis was successfully described by a Fickian model. When ISIS was used as a solvent Fickian behaviour was only obtained across isolated stratum corneum suggesting that the hydrophilic layers of the epidermis interfere with the permeation of the hydrophobic ISIS. The diffusion coefficients of CNP across epidermis in the different solvents were not significantly different. Using chemometric data analysis diffusion profiles for the solvents were deconvoluted from that of the skin and modelled. Each of these solvents was found to diffuse at a faster rate across the skin than CNP. DPPG considerably increased the concentration of CNP in the stratum corneum in comparison with the other solvents indicating strong penetration enhancer potential. In contrast IPM produced a similar CNP concentration in the stratum corneum to water with ISIS resulting in a lower CNP concentration suggesting negligible enhancement and penetration retardation effects for these two solvents respectively. Copyright © 2013 Elsevier B.V. All rights reserved.

Synthesis and Biological Evaluation of Brain-Specific Anti-RNA Viral Agents

DTIC Science & Technology

1990-03-31

water (200 iL). It was dried over sodium sulfate and the solvent was removed under reduced pressure. The resulting oil was dissolved in a minimum...The organic extracts were washed with NaHCO3 (2 x 200 mL), water (200 mL) and dried over sodium sulfate . The solvent was removed in vacuo and the...chloroform. The combined organic extracts were washed with 2 x 250 mL cold deionised water, dried ( sodium sulfate ) and removed under reduced pressure to

MIPs in Aqueous Environments.

PubMed

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.

Enthalpies of solvation for dopamine hydrochloride in water-ethanol solutions

NASA Astrophysics Data System (ADS)

Vandyshev, V. N.; Ledenkov, S. F.; Molchanov, A. S.

2012-10-01

The enthalpies of dissolution of dopamine hydrochloride (H2Dop · HCl) in water-ethanol solvents containing from 0 to 0.8 mole fraction of ethanol are measured by calorimetry at 298.15 K. Standard enthalpies of transfer (Δtr H ∘) for the molecular (H2Dop) and cationic (H3Dop+) forms of dopamine from water into binary solvents are calculated from the obtained data. The enthalpies of transfer of H3Dop+ cation are determined from the enthalpies of dissolution of H2Dop · HCl using the familiar method of separating the molar quantities into ionic contributions (Ph4P+ = BPh{4/-}), and by an original alternative procedure. The effect of the composition of the binary solvent on the solvation of dopamine is considered.

Oxidation of white phosphorus by peroxides in water

NASA Astrophysics Data System (ADS)

Abdreimova, R. R.; Akbaeva, D. N.; Polimbetova, G. S.

2017-10-01

A mixture of hypophosphorous, phosphorous, and phosphoric acids is formed during the anaerobic oxidation of white phosphorus by peroxides [ROOH; R = H, 3-ClC6H4CO, (CH3)3C] in water. The rate of reactions grows considerably upon adding nonpolar organic solvents. The activity series of peroxides and solvents are determined experimentally. NMR spectroscopy shows that the main product of the reaction is phosphorous acid, regardless of the nature of the peroxide and solvent. A radical mechanism of oxidation of white phosphorus by peroxides in water is proposed. It is initiated by the homolysis of peroxide with the formation of HO• radicals that are responsible for the homolytic opening of phosphoric tetrahedrons. Further oxidation and stages of the hydrolysis of intermediate phosphorus-containing compounds yield products of the reaction.

Recovery of catechin compounds from Korean tea by solvent extraction.

PubMed

Row, Kyung Ho; Jin, Yinzhe

2006-03-01

Catechin compounds from Korean green tea as potential sources of anticancer and antioxidant components were target materials in this work. The methodologies of solvent extraction and partition were utilized to recover catechin compounds from green tea. The optimum experimental condition was obtained by optimizing operating factors, such as, the extraction solvent, extraction time and operating temperature. After extracting the green tea with water at 80 degrees C for 40 min, the extract was partitioned with water/chloroform, which was best suited to remove caffeine impurity from the extract. Further, the resulting extract was partitioned water/ethyl acetate to deeply purify the catechin compounds of EGC, EC, EGCG and ECG. The experimental result in this work could be extended to preparative HPLC to obtain EGCG on commercial scale.

Towards ultra-fast solvent evaporation, the development of a computer controlled solvent vapor annealing chamber

NASA Astrophysics Data System (ADS)

Nelson, Gunnar; Wong, J.; Drapes, C.; Grant, M.; Baruth, A.

Despite the promise of cheap and fast nanoscale ordering of block polymer thin films via solvent vapor annealing, a standardized, scalable production scheme remains elusive. Solvent vapor annealing exposes a nano-thin film to the vapors of one or more solvents with the goal of forming a swollen and mobile state to direct the self-assembly process by tuning surface energies and mediating unfavorable chain interactions. We have shown that optimized annealing conditions, where kinetic and thermal properties for crystal growth are extremely fast (<1s), exist at solvent concentrations just below the order-disorder transition of the film. However, when investigating the propagation of a given morphology into the bulk of a film during drying, the role of solvent evaporation comes under great scrutiny. During this process, the film undergoes a competition between two fronts; phase separation and kinetic trapping. Recent results in both theory and experiment point toward this critical element in controlling the resultant morphologies; however, no current method includes a controllable solvent evaporation rate at ultra-fast time scales. We report on a computer-controlled, pneumatically actuated chamber that provides control over solvent evaporation down to 15 ms. Furthermore, in situ spectral reflectance monitors solvent concentration with 10 ms temporal resolution and reveals several possible evaporation trajectories, ranging from linear to exponential to logarithmic. Funded by Dr. Randolph Ferlic Summer Research Scholarship and NASA Nebraska Space Grant.

Solvent and process for recovery of hydroxide from aqueous mixtures

DOEpatents

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.

Gas chromatography/isotope ratio mass spectrometry: analysis of methanol, ethanol and acetic acid by direct injection of aqueous alcoholic and acetic acid samples.

PubMed

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.

Transport of Proteins Dissolved in Organic Solvents Across Biomimetic Membranes

NASA Astrophysics Data System (ADS)

Bromberg, Lev E.; Klibanov, Alexander M.

1995-02-01

Using lipid-impregnated porous cellulose membranes as biomimetic barriers, we tested the hypothesis that to afford effective transmembrane transfer of proteins and nucleic acids, the vehicle solvent should be able to dissolve both the biopolymers and the lipids. While the majority of solvents dissolve one or the other, ethanol and methanol were found to dissolve both, especially if the protein had been lyophilized from an aqueous solution of a pH remote from the protein's isoelectric point. A number of proteins, as well as RNA and DNA, dissolved in these alcohols readily crossed the lipidized membranes, whereas the same biopolymers placed in nondissolving solvents (e.g., hexane and ethyl acetate) or in those unable to dissolve lipids (e.g., water and dimethyl sulfoxide) exhibited little transmembrane transport. The solubility of biopolymers in ethanol and methanol was further enhanced by complexation with detergents and poly(ethylene glycol); significant protein and nucleic acid transport through the lipidized membranes was observed from these solvents but not from water.

Characteristics and antioxidant of Ulva intestinalis sulphated polysaccharides extracted with different solvents.

PubMed

Peasura, Napassorn; Laohakunjit, Natta; Kerdchoechuen, Orapin; Wanlapa, Sorada

2015-11-01

Ulva intestinalis, a tubular green seaweed, is a rich source of nutrient, especially sulphated polysaccharides. Sulphated polysaccharides from U. intestinalis were extracted with distilled water, 0.1N HCl, and 0.1N NaOH at 80°C for 1, 3, 6, 12, and 24h to study the effect of the extraction solvent and time on their chemical composition and antioxidant activity. Different types of solvents and extraction time had a significant influence on the chemical characteristics and antioxidant activity (p<0.05). Monosaccharide composition and FT-IR spectra analyses revealed that sulphated polysaccharides from all solvent extractions have a typical sugar backbone (glucose, rhamnose, and sulphate attached at C-2 or C-3 of rhamnose). Sulphated polysaccharides extracted with acid exhibited greater antioxidant activity than did those extracted with distilled water and alkali. The results indicated that solvent extraction could be an efficacious method for enhancing antioxidant activity by distinct molecular weight and chemical characteristic of sulphated polysaccharides. Copyright © 2015 Elsevier B.V. All rights reserved.

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

PubMed

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

2017-10-01

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

Phase Behavior of a Single Structured Ionomer Chain in Solution

DOE PAGES

Aryal, Dipak; Etampawala, Thusitha; Perahia, Dvora; ...

2014-08-14

Structured polymers offer a means to tailor transport pathways within mechanically stable manifolds. Here we examine the building block of such a membrane, namely a single large pentablock co-polymer that consist of a center block of a randomly sulfonated polystyrene, designed for transport, tethered to poly-ethylene-r-propylene and end-capped by poly-t-butyl styrene, for mechanical stability,using molecular dynamics simulations. The polymer structure in a cyclohexane-heptane mixture, a technologically viable solvent, and in water, a poor solvent for all segments and a ubiquitous substance is extracted. In all solvents the pentablock collapsed into nearly spherical aggregates where the ionic block is segregated. Inmore » hydrophobic solvents, the ionic block resides in the center, surrounded by swollen intermix of flexible and end blocks. In water all blocks are collapsed with the sulfonated block residing on the surface. Our results demonstrate that solvents drive different local nano-segregation, providing a gateway to assemble membranes with controlled topology.« less

Method for making surfactant-templated thin films

DOEpatents

Brinker, C. Jeffrey; Lu, Yunfeng; Fan, Hong You

2010-08-31

An evaporation-induced self-assembly method to prepare a porous, surfactant-templated, thin film by mixing a silica sol, a solvent, a surfactant, and an interstitial compound, evaporating a portion of the solvent to form a liquid, crystalline thin film mesophase material, and then removal of the surfactant template. Coating onto a substrate produces a thin film with the interstitial compound either covalently bonded to the internal surfaces of the ordered or disordered mesostructure framework or physically entrapped within the ordered or disordered mesostructured framework. Particles can be formed by aerosol processing or spray drying rather than coating onto a substrate. The selection of the interstitial compound provides a means for developing thin films for applications including membranes, sensors, low dielectric constant films, photonic materials and optical hosts.

Method for making surfactant-templated thin films

DOEpatents

Brinker, C. Jeffrey; Lu, Yunfeng; Fan, Hongyou

2002-01-01

An evaporation-induced self-assembly method to prepare a porous, surfactant-templated, thin film by mixing a silica sol, a solvent, a surfactant, and an interstitial compound, evaporating a portion of the solvent to form a liquid, crystalline thin film mesophase material, and then removal of the surfactant template. Coating onto a substrate produces a thin film with the interstitial compound either covalently bonded to the internal surfaces of the ordered or disordered mesostructure framework or physically entrapped within the ordered or disordered mesostructured framework. Particles can be formed by aerosol processing or spray drying rather than coating onto a substrate. The selection of the interstitial compound provides a means for developing thin films for applications including membranes, sensors, low dielectric constant films, photonic materials and optical hosts.

What factors control dimerization of coniferyl alcohol?

Treesearch

Carl J. Houtman

1999-01-01

Data suggest that the dimerization of coniferyl alcohol is not under thermodynamic control. In this study, molecular dynamics calculations were used to estimate the effect of the solvent environment. In water, the coniferyl alcohol radicals were forced to associate by the formation of a solvent cage. In glycerol, the solvent cage effect appeared to be absent. These...

SOLVENT EXTRACTION OF URANIUM VALUES

DOEpatents

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/.

Non-aqueous liquid compositions comprising ion exchange polymers

DOEpatents

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.

Non-aqueous liquid compositions comprising ion exchange polymers

DOEpatents

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.

[Supercritical and near-critical fluid solvents assisted reaction and separation processes].

PubMed

Song, R; Zeng, J; Zhong, B

2001-11-01

The tunability of supercritical and near-critical fluid (S/NCF) solvents offers environmental improvements and economic advantages from improved performances and flexibility for separation and reaction processes through density changes or cosolvents. The paper reviews the sustainable reaction and separation processes in S/NCF solvents such as supercritical carbon dioxide and near-critical water.

Melaminium nitrate–melamine–water (1/1/1)

PubMed Central

Adam, Farook; Lin, Sek Kei; Hello, Kasim Mohammed; Hemamalini, Madhukar; Fun, Hoong-Kun

2010-01-01

In the crystal structure of the title salt, C3H7N6 +·NO3 −·C3H6N6·H2O, the asymmetric unit consists of two neutral melamine (1,3,5-triazine-2,4,6-triamine) mol­ecules, two melaminium cations, two nitrate anions and two solvent water mol­ecules. One of the nitrate anions is disordered over two sets of positions, with a refined occupancy ratio of 0.909 (3):0.091 (3). The cations and neutral mol­ecules are approximately planar, with maximum deviations of 0.018 (2), 0.024 (2), 0.019 (2) and 0.007 (2) Å for each, respectively. In the crystal structure, melaminium cations and netural melamine mol­ecules self-assemble via N—H⋯N hydrogen bonds to form a supra­molecular hexa­gonal-shaped motif. In addition, the nitrate anions and water mol­ecules are connected by N—H⋯O hydrogen bonds to form a three-dimensional network. PMID:21589188

Crystal structure of tetra-kis-(μ3-2-{[1,1-bis-(hy-droxy-meth-yl)-2-oxidoeth-yl]imino-meth-yl}phenolato)tetra-copper(II) ethanol monosolvate 2.5-hydrate.

PubMed

Wang, Weilun; Ran, Jingwen

2015-05-01

The title compound, [Cu4(C11H13NO4)4]·CH3CH2OH·2.5H2O, is an electronically neutral tetra-nuclear copper(II) complex with a cubane-like Cu4O4 core. The complete molecule has point group symmetry 2. The phenol hy-droxy group and one of the three alcohol hy-droxy groups of each 2-{[tris-(hy-droxy-meth-yl)meth-yl]imino-meth-yl}phenol ligand are depro-ton-ated, while the secondary amine and the other two hy-droxy groups remain unchanged. The Cu(II) atoms in the Cu4O4 core are connected by four μ3-O atoms from the deprotonated alcohol hy-droxy groups. Each of the penta-coordinated Cu(II) ions has an NO4 distorted square-pyramidal environment through coordination to the tridentate Schiff base ligands. The Cu-N/O bond lengths span the range 1.902 (4)-1.955 (4) Å, similar to values reported for related structures. There are O-H⋯O hydrogen-bond inter-actions between the complex molecules and the ethanol and water solvent molecules, leading to the formation of a three-dimensional network. The ethanol solvent molecule is disordered about a twofold rotation axis. One of the two independent water molecules is also located on this twofold rotation axis and shows half-occupancy.

Water-Based Pressure-Sensitive Paints

NASA Technical Reports Server (NTRS)

Jordan, Jeffrey D.; Watkins, A. Neal; Oglesby, Donald M.; Ingram, JoAnne L.

2006-01-01

Water-based pressure-sensitive paints (PSPs) have been invented as alternatives to conventional organic-solvent-based pressure-sensitive paints, which are used primarily for indicating distributions of air pressure on wind-tunnel models. Typically, PSPs are sprayed onto aerodynamic models after they have been mounted in wind tunnels. When conventional organic-solvent-based PSPs are used, this practice creates a problem of removing toxic fumes from inside the wind tunnels. The use of water-based PSPs eliminates this problem. The waterbased PSPs offer high performance as pressure indicators, plus all the advantages of common water-based paints (low toxicity, low concentrations of volatile organic compounds, and easy cleanup by use of water).

Solubility and thermodynamics of apremilast in different mono solvents: Determination, correlation and molecular interactions.

PubMed

Shakeel, Faiyaz; Haq, Nazrul; Alanazi, Fars K; Alsarra, Ibrahim A

2017-05-15

The solubility data of recently launched poorly soluble antipsoriatic drug apremilast (APM) in any mono solvent or cosolvent mixtures with respect to temperature are not available in literature. Hence, in this research work, the solubility of APM in twelve different mono solvents namely "water, methanol, ethanol, isopropanol (IPA), ethylene glycol (EG), propylene glycol (PG), 1-butanol, 2-butanol, ethyl acetate (EA), dimethyl sulfoxide (DMSO), polyethylene glycol-400 (PEG-400) and Transcutol ® " was determined at temperatures "T=298.2K to 318.2K" and pressure "p=0.1 MPa". Eexperimental solubilities of APM in mole fraction were determined by a static equilibrium method using high performance liquid chromatography at 254nm. Experimental solubilities of APM in mole fraction were correlated well with "Van't Hoff and Apelblat models". The solubilities of APM in mole fraction were recorded highest in DMSO (9.91×10 -2 ), followed by EA (2.54×10 -2 ), Transcutol (2.51×10 -2 ), PEG-400 (2.16×10 -2 ),PG (4.01×10 -3 ), EG (1.61×10 -3 ), IPA (4.96×10 -4 ), 1-butanol (4.18×10 -4 ), 2-butanol (3.91×10 -4 ), methanol (2.25×10 -4 ), ethanol (2.20×10 -4 ) and water (1.29×10 -6 ) at "T=318.2K" and similar results were also obtained at each temperature evaluated. The molecular interactions between solute and solvent molecules were evaluated by the determination of activity coefficients. Based on activity coefficients, the higher solute-solvents molecular interactions were recorded in APM-DMSO, APM-EA, APM-Transcutol and APM-PEG-400 in comparison with other combination of solute and solvents. "Apparent standard thermodynamic parameters" of APM indicated an "endothermic and entropy-driven dissolution" of APM in all mono solvents evaluated. Based on these results, APM was proposed as freely soluble in DMSO, EA and Transcutol, sparingly soluble in PEG0-400, slightly soluble in methanol, ethanol, IPA, EG, PG, 1-butanol and 2-butanol and practically insoluble in water. Hence, DMSO, EA and Transcutol were selected as the best solvents and water and ethanol were selected as the anti-solvents for APM. Copyright © 2017 Elsevier B.V. All rights reserved.

Molecular description of the LCST behavior of an elastin-like polypeptide.

PubMed

Li, Nan K; García Quiroz, Felipe; Hall, Carol K; Chilkoti, Ashutosh; Yingling, Yaroslava G

2014-10-13

Elastin-like polypeptides (ELPs) with the repeat sequence of VPGVG are widely used as a model system for investigation of lower critical solution temperature (LCST) transition behavior. In this paper, the effect of temperature on the structure, dynamics and association of (VPGVG)18 in aqueous solution is investigated using atomistic molecular dynamics simulations. Our simulations show that as the temperature increases the ELP backbones undergo gradual conformational changes, which are attributed to the formation of more ordered secondary structures such as β-strands. In addition, increasing temperature changes the hydrophobicity of the ELP by exposure of hydrophobic valine-side chains to the solvent and hiding of proline residues. Based on our simulations, we conclude that the transition behavior of (VPGVG)18 can be attributed to a combination of thermal disruption of the water network that surrounds the polypeptide, reduction of solvent accessible surface area of the polypeptide, and increase in its hydrophobicity. Simulations of the association of two (VPGVG)18 molecules demonstrated that the observed gradual changes in the structural properties of the single polypeptide chain are enough to cause the aggregation of polypeptides above the LCST. These results lead us to propose that the LCST phase behavior of poly(VPGVG) is a collective phenomenon that originates from the correlated gradual changes in single polypeptide structure and the abrupt change in properties of hydration water around the peptide and is a result of a competition between peptide-peptide and peptide-water interactions. This is a computational study of an important intrinsically disordered peptide system that provides an atomic-level description of structural features and interactions that are relevant in the LCST phase behavior.

Anion exchange membranes composed of a poly(2,6-dimethyl-1,4-phenylene oxide) random copolymer functionalized with a bulky phosphonium cation

DOE PAGES

Liu, Ye; Zhang, Bingzi; Kinsinger, Corey L.; ...

2016-01-22

A random copolymer, tris(2,4,6-trimethoxyphenyl) phosphonium functionalized poly(2,6-dimethyl-1,4-phenylene oxide) (PPO-TPQP) was cast from three different solvents: dimethyl sulfoxide (DMSO), ethyl lactate, or a 41:59 vol% mixture of DMSO and ethyl lactate. Solvents were selected via analysis of the Hansen solubility parameters to vary the phase separation of the polymer in the films. An optimized mixture of DMSO and ethyl lactate chosen for film fabrication and this film was contrasted with films cast from the neat constituent solvents. Atomic force microscopy identified domains from nanometer to tens of nanometer sizes, while the light microscopy showed features on the order of micron. SAXSmore » revealed a cation scattering peak with a d-spacing from 7 to 15 Å. Trends in conductivity and water diffusion for the membranes vary depending on the solvent from which they are cast. The mixed solvent cast membrane shows a linear Arrhenius behavior indicating fully dissociated cationic/anionic groups, and has the highest bromide conductivity of 3 mS/cm at 95% RH, 90 °C. The ethyl lactate cast membrane shows a linear Arrhenius relation in conductivity, but a Vogel-Tamman-Fulcher behavior in its water self-diffusion. While water increases bromide dissociation, water and bromide transport in these films seems to be decoupled. Lastly, this is particularly true for the film cast from ethyl lactate.« less

Anion exchange membranes composed of a poly(2,6-dimethyl-1,4-phenylene oxide) random copolymer functionalized with a bulky phosphonium cation

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

Liu, Ye; Zhang, Bingzi; Kinsinger, Corey L.

A random copolymer, tris(2,4,6-trimethoxyphenyl) phosphonium functionalized poly(2,6-dimethyl-1,4-phenylene oxide) (PPO-TPQP) was cast from three different solvents: dimethyl sulfoxide (DMSO), ethyl lactate, or a 41:59 vol% mixture of DMSO and ethyl lactate. Solvents were selected via analysis of the Hansen solubility parameters to vary the phase separation of the polymer in the films. An optimized mixture of DMSO and ethyl lactate chosen for film fabrication and this film was contrasted with films cast from the neat constituent solvents. Atomic force microscopy identified domains from nanometer to tens of nanometer sizes, while the light microscopy showed features on the order of micron. SAXSmore » revealed a cation scattering peak with a d-spacing from 7 to 15 A. Trends in conductivity and water diffusion for the membranes vary depending on the solvent from which they are cast. The mixed solvent cast membrane shows a linear Arrhenius behavior indicating fully dissociated cationic/anionic groups, and has the highest bromide conductivity of 3 mS/cm at 95% RH, 90 degrees C. The ethyl lactate cast membrane shows a linear Arrhenius relation in conductivity, but a Vogel-Tamman-Fulcher behavior in its water self-diffusion. While water increases bromide dissociation, water and bromide transport in these films seems to be decoupled. This is particularly true for the film cast from ethyl lactate.« less

Anion exchange membranes composed of a poly(2,6-dimethyl-1,4-phenylene oxide) random copolymer functionalized with a bulky phosphonium cation

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

Liu, Ye; Zhang, Bingzi; Kinsinger, Corey L.

A random copolymer, tris(2,4,6-trimethoxyphenyl) phosphonium functionalized poly(2,6-dimethyl-1,4-phenylene oxide) (PPO-TPQP) was cast from three different solvents: dimethyl sulfoxide (DMSO), ethyl lactate, or a 41:59 vol% mixture of DMSO and ethyl lactate. Solvents were selected via analysis of the Hansen solubility parameters to vary the phase separation of the polymer in the films. An optimized mixture of DMSO and ethyl lactate chosen for film fabrication and this film was contrasted with films cast from the neat constituent solvents. Atomic force microscopy identified domains from nanometer to tens of nanometer sizes, while the light microscopy showed features on the order of micron. SAXSmore » revealed a cation scattering peak with a d-spacing from 7 to 15 Å. Trends in conductivity and water diffusion for the membranes vary depending on the solvent from which they are cast. The mixed solvent cast membrane shows a linear Arrhenius behavior indicating fully dissociated cationic/anionic groups, and has the highest bromide conductivity of 3 mS/cm at 95% RH, 90 °C. The ethyl lactate cast membrane shows a linear Arrhenius relation in conductivity, but a Vogel-Tamman-Fulcher behavior in its water self-diffusion. While water increases bromide dissociation, water and bromide transport in these films seems to be decoupled. Lastly, this is particularly true for the film cast from ethyl lactate.« less

The impact of mixed solvents on the complexation thermodynamics of Eu(III) by simple carboxylate and amino carboxylate ligands

DOE PAGES

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

Deep Eutectic Solvents as Efficient Media for the Extraction and Recovery of Cynaropicrin from Cynara cardunculus L. Leaves.

PubMed

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.

The impact of mixed solvents on the complexation thermodynamics of Eu(III) by simple carboxylate and amino carboxylate ligands

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

Strongly Iridescent Hybrid Photonic Sensors Based on Self-Assembled Nanoparticles for Hazardous Solvent Detection.

PubMed

Sato, Ayaka; Ikeda, Yuya; Yamaguchi, Koichi; Vohra, Varun

2018-03-16

Facile detection and the identification of hazardous organic solvents are essential for ensuring global safety and avoiding harm to the environment caused by industrial wastes. Here, we present a simple method for the fabrication of silver-coated monodisperse polystyrene nanoparticle photonic structures that are embedded into a polydimethylsiloxane (PDMS) matrix. These hybrid materials exhibit a strong green iridescence with a reflectance peak at 550 nm that originates from the close-packed arrangement of the nanoparticles. This reflectance peak measured under Wulff-Bragg conditions displays a 20 to 50 nm red shift when the photonic sensors are exposed to five commonly employed and highly hazardous organic solvents. These red-shifts correlate well with PDMS swelling ratios using the various solvents, which suggests that the observable color variations result from an increase in the photonic crystal lattice parameter with a similar mechanism to the color modulation of the chameleon skin. Dynamic reflectance measurements enable the possibility of clearly identifying each of the tested solvents. Furthermore, as small amounts of hazardous solvents such as tetrahydrofuran can be detected even when mixed with water, the nanostructured solvent sensors we introduce here could have a major impact on global safety measures as innovative photonic technology for easily visualizing and identifying the presence of contaminants in water.

Water extractable arabinoxylan aerogels prepared by supercritical CO2 drying.

PubMed

Marquez-Escalante, Jorge; Carvajal-Millan, Elizabeth; Miki-Yoshida, Mario; Alvarez-Contreras, Lorena; Toledo-Guillén, Alma Rosa; Lizardi-Mendoza, Jaime; Rascón-Chu, Agustín

2013-05-14

Water extractable arabinoxylan (WEAX) aerogels were prepared by extracting the solvent from the alcogels (WEAX hydrogels with an alcohol as the solvent) with carbon dioxide under supercritical conditions. WEAX aerogels were characterized using scanning electron microscopy and adsorption and desorption nitrogen isotherms. The micrographs indicate a heterogeneous porous network structure in WEAX aerogel. Adsorption/desorption nitrogen isotherms of this material were type IV, which confirm that this material possess a mesoporous structure. WEAX aerogels rehydration capability was evaluated and the water absorption mechanism was determined. The WEAX aerogels water absorption mechanism was non-Fickian (n = 0.54).

Enhanced Furfural Yields from Xylose Dehydration in the gamma-Valerolactone/Water Solvent System at Elevated Temperatures.

PubMed

Sener, Canan; Motagamwala, Ali Hussain; Alonso, David Martin; Dumesic, James

2018-05-18

High yields of furfural (>90%) were achieved from xylose dehydration in a sustainable solvent system composed of -valerolactone (GVL), a biomass derived solvent, and water. It is identified that high reaction temperatures (e.g., 498 K) are required to achieve high furfural yield. Additionally, it is shown that the furfural yield at these temperatures is independent of the initial xylose concentration, and high furfural yield is obtained for industrially relevant xylose concentrations (10 wt%). A reaction kinetics model is developed to describe the experimental data obtained with solvent system composed of 80 wt% GVL and 20 wt% water across the range of reaction conditions studied (473 - 523 K, 1-10 mM acid catalyst, 66 - 660 mM xylose concentration). The kinetic model demonstrates that furfural loss due to bimolecular condensation of xylose and furfural is minimized at elevated temperature, whereas carbon loss due to xylose degradation increases with increasing temperature. Accordingly, the optimal temperature range for xylose dehydration to furfural in the GVL/H2O solvent system is identified to be from 480 to 500 K. Under these reaction conditions, furfural yield of 93% is achieved at 97% xylan conversion from lignocellulosic biomass (maple wood). © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Optimization and determination of Cd (II) in different environmental water samples with dispersive liquid-liquid microextraction preconcentration combined with inductively coupled plasma optical emission spectrometry.

PubMed

Salahinejad, Maryam; Aflaki, Fereydoon

2011-06-01

Dispersive liquid-liquid microextraction followed by inductively coupled plasma-optical emission spectrometry has been investigated for determination of Cd(II) ions in water samples. Ammonium pyrrolidine dithiocarbamate was used as chelating agent. Several factors influencing the microextraction efficiency of Cd (II) ions such as extracting and dispersing solvent type and their volumes, pH, sample volume, and salting effect were optimized. The optimization was performed both via one variable at a time, and central composite design methods and the optimum conditions were selected. Both optimization methods showed nearly the same results: sample size 5 mL; dispersive solvent ethanol; dispersive solvent volume 2 mL; extracting solvent chloroform; extracting solvent volume 200 [Formula: see text]L; pH and salt amount do not affect significantly the microextraction efficiency. The limits of detection and quantification were 0.8 and 2.5 ng L( - 1), respectively. The relative standard deviation for five replicate measurements of 0.50 mg L( - 1) of Cd (II) was 4.4%. The recoveries for the spiked real samples from tap, mineral, river, dam, and sea waters samples ranged from 92.2% to 104.5%.

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

ERIC Educational Resources Information Center

Seng, Set; Kita, Masakazu; Sugihara, Reiko

2007-01-01

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

Solid-phase microextraction of hydrocarbons from water in a centrifuge

NASA Astrophysics Data System (ADS)

Ryabov, A. Yu.; Chuikin, A. V.; Velikov, A. A.

2016-06-01

The results of our study of solid-phase microextraction of substances using a centrifuge for determining the microquantities of hydrocarbon impurities in water are presented. The cartridge diameter, sorbent mass, and solvent volume were shown to affect the percent extraction of substances and the analytical signal intensity. The relationship between the cartridge geometry, the sorbent mass, and the solvent volume was considered.

Selective hydrogenation of amides to alcohols in water solvent over a heterogeneous CeO2-supported Ru catalyst.

PubMed

Tamura, Masazumi; Ishikawa, Susumu; Betchaku, Mii; Nakagawa, Yoshinao; Tomishige, Keiichi

2018-06-20

CeO2-supported Ru (Ru/CeO2) worked as an effective and reusable heterogeneous catalyst for the selective dissociation of the C-N bond in amides, particularly primary amides, with H2 in water solvent at low reaction temperature of 333 K, and high yields of the corresponding alcohols were obtained from primary amides.

Water quality criteria for colored smokes: Solvent Yellow 33, Final report. [Contains glossary

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

Davidson, K.A.; Hovatter, P.S.

1987-11-01

The available data on the environmental fate, aquatic toxicity, and mammalian toxicity of Solvent Yellow 33, a quinoline dye used in colored smoke grenades, were reviewed. The US Environmental Protection Agency (USEPA) guidelines were used in an attempt to generate water quality criteria for the protection of aquatic life and its use and of human health. 87 refs., 2 figs., 13 tabs.

CO2-Binding Organic Liquids Gas Capture with Polarity-Swing-Assisted Regeneration Full Technology Feasibility Study B1 - Solvent-based Systems

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

Heldebrant, David J

PNNL, Fluor Corporation and Queens University (Kingston, ON) successfully completed a three year comprehensive study of the CO2BOL water-lean solvent platform with Polarity Swing Assisted Regeneration (PSAR). This study encompassed solvent synthesis, characterization, environmental toxicology, physical, thermodynamic and kinetic property measurements, Aspen Plus™ modeling and bench-scale testing of a candidate CO2BOL solvent molecule. Key Program Findings The key program findings are summarized as follows: • PSAR favorably reduced stripper duties and reboiler temperatures with little/no impact to absorption column • >90% CO2 capture was achievable at reasonable liquid-gas ratios in the absorber • High rich solvent viscosities (up to 600more » cP) were successfully demonstrated in the bench-scale system. However, the projected impacts of high viscosity to capital cost and operational limits compromised the other levelized cost of electricity benefits. • Low thermal conductivity of organics significantly increased the required cross exchanger surface area, and potentially other heat exchange surfaces. • CO2BOL had low evaporative losses during bench-scale testing • There was no evidence of foaming during bench scale testing • Current CO2BOL formulation costs project to be $35/kg • Ecotoxicity (Water Daphnia) was comparable between CO2BOL and MEA (169.47 versus 103.63 mg/L) • Full dehydration of the flue gas was determined to not be economically feasible. However, modest refrigeration (13 MW for the 550 MW reference system) was determined to be potentially economically feasible, and still produce a water-lean condition for the CO2BOLs (5 wt% steady-state water loading). • CO2BOLs testing with 5 wt% water loading did not compromise anhydrous performance behavior, and showed actual enhancement of CO2 capture performance. • Mass transfer of CO2BOLs was not greatly impeded by viscosity • Facile separation of antisolvent from lean CO2BOL was demonstrated on the bench cart • No measurable solvent degradation was observed over 4 months of testing – even with 5 wt% water present« less

Separation by solvent extraction

DOEpatents

Holt, Jr., Charles H.

1976-04-06

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

Enhanced ion signals in desorption electrospray ionization using surfactant spray solutions.

PubMed

Badu-Tawiah, Abraham; Cooks, R Graham

2010-08-01

Solvent optimization is an important procedure in desorption electrospray ionization (DESI) and in this study the effects of solvent surface tension are explored. Data are presented for methanol/water/surfactant solvent systems, which show increases in ion signals of more than an order of magnitude when low concentrations of surfactants are added to the standard methanol/water (1:1) spray solvent. Examples of analytes tested include food chemicals, peptides, pharmaceuticals, and drugs of abuse. The improvement in ion intensity is mainly attributed to the effect of surface tension in producing smaller spray droplets, which are shown to cover a larger surface area. Surfactant-containing spray solutions allowed extension of DESI-MS analysis to previously intractable analytes like melamine and highly hydrophobic compounds like the sudan dyes. Copyright 2010 American Society for Mass Spectrometry. Published by Elsevier Inc. All rights reserved.

Nano porous silicon microcavity sensor for determination organic solvents and pesticide in water

NASA Astrophysics Data System (ADS)

Pham, Van Hoi; Van Nguyen, Thuy; Nguyen, The Anh; Pham, Van Dai; Bui, Huy

2014-12-01

In this paper we present a sensing method using nano-porous silicon microcavity sensor, which was developed in order to obtain simultaneous determination of two volatile substances with different solvent concentrations as well as very low pesticide concentration in water. The temperature of the solution and the velocity of the air stream flowing through the solution have been used to control the response of the sensor for different solvent solutions. We study the dependence of the cavity-resonant wavelength shift on solvent concentration, velocity of the airflow and solution temperature. The wavelength shift depends linearly on concentration and increases with solution temperature and velocity of the airflow. The dependence of the wavelength shift on the solution temperature in the measurement contains properties of the temperature dependence of the solvent vapor pressure, which characterizes each solvent. As a result, the dependence of the wavelength shift on the solution temperature discriminates between solutions of ethanol and acetone with different concentrations. This suggests a possibility for the simultaneous determination of the volatile substances and their concentrations. On the other hand, this method is able to detect the presence of atrazine pesticide by the shift of the resonant wavelength, with good sensitivity (0.3 nm pg-1 ml) and limit of detection (LOD) (0.8-1.4 pg ml-1), that we tested for concentrations in the range from 2.15 to 21.5 pg ml-1, which is the range useful for monitoring acceptable water for human consumption.

Aminosilicone solvent recovery methods and systems

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

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

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

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

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

Clark, Sue B.

2016-10-31

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

The Biodegradation of TNT in Enhanced Soil and Compost Systems

DTIC Science & Technology

1978-01-01

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

Carbon nanotube embedded PVDF membranes: Effect of solvent composition on the structural morphology for membrane distillation

NASA Astrophysics Data System (ADS)

Mapunda, Edgar C.; Mamba, Bhekie B.; Msagati, Titus A. M.

2017-08-01

Rapid population increase, growth in industrial and agricultural sectors and global climate change have added significant pressure on conventional freshwater resources. Tapping freshwater from non-conventional water sources such as desalination and wastewater recycling is considered as sustainable alternative to the fundamental challenges of water scarcity. However, affordable and sustainable technologies need to be applied for the communities to benefit from the treatment of non-conventional water source. Membrane distillation is a potential desalination technology which can be used sustainably for this purpose. In this work multi-walled carbon nanotube embedded polyvinylidene fluoride membranes for application in membrane distillation desalination were prepared via non-solvent induced phase separation method. The casting solution was prepared using mixed solvents (N, N-dimethylacetamide and triethyl phosphate) at varying ratios to study the effect of solvent composition on membrane morphological structures. Membrane morphological features were studied using a number of techniques including scanning electron microscope, atomic force microscope, SAXSpace tensile strength analysis, membrane thickness, porosity and contact angle measurements. It was revealed that membrane hydrophobicity, thickness, tensile strength and surface roughness were increasing as the composition of N, N-dimethylacetamide in the solvent was increasing with maximum values obtained between 40 and 60% N, N-dimethylacetamide. Internal morphological structures were changing from cellular structures to short finger-like and sponge-like pores and finally to large macro void type of pores when the amount of N, N-dimethylacetamide in the solvent was changed from low to high respectively. Multi-walled carbon nanotube embedded polyvinylidene fluoride membranes of desired morphological structures and physical properties can be synthesized by regulating the composition of solvents used to prepare the casting solution.

Gas-liquid transfer data used to analyze hydrophobic hydration and find the nature of the Kauzmann-Tanford hydrophobic factor.

PubMed

Baldwin, Robert L

2012-05-08

Hydrophobic free energy for protein folding is currently measured by liquid-liquid transfer, based on an analogy between the folding process and the transfer of a nonpolar solute from water into a reference solvent. The second part of the analogy (transfer into a nonaqueous solvent) is dubious and has been justified by arguing that transfer out of water probably contributes the major part of the free energy change. This assumption is wrong: transfer out of water contributes no more than half the total, often less. Liquid-liquid transfer of the solute from water to liquid alkane is written here as the sum of 2 gas-liquid transfers: (i) out of water into vapor, and (ii) from vapor into liquid alkane. Both gas-liquid transfers have known free energy values for several alkane solutes. The comparable values of the two different transfer reactions are explained by the values, determined in 1991 for three alkane solutes, of the cavity work and the solute-solvent interaction energy. The transfer free energy is the difference between the positive cavity work and the negative solute-solvent interaction energy. The interaction energy has similar values in water and liquid alkane that are intermediate in magnitude between the cavity work in water and in liquid alkane. These properties explain why the transfer free energy has comparable values (with opposite signs) in the two transfers. The current hydrophobic free energy is puzzling and poorly defined and needs a new definition and method of measurement.

Gas-liquid transfer data used to analyze hydrophobic hydration and find the nature of the Kauzmann-Tanford hydrophobic factor

PubMed Central

Baldwin, Robert L.

2012-01-01

Hydrophobic free energy for protein folding is currently measured by liquid-liquid transfer, based on an analogy between the folding process and the transfer of a nonpolar solute from water into a reference solvent. The second part of the analogy (transfer into a nonaqueous solvent) is dubious and has been justified by arguing that transfer out of water probably contributes the major part of the free energy change. This assumption is wrong: transfer out of water contributes no more than half the total, often less. Liquid-liquid transfer of the solute from water to liquid alkane is written here as the sum of 2 gas-liquid transfers: (i) out of water into vapor, and (ii) from vapor into liquid alkane. Both gas-liquid transfers have known free energy values for several alkane solutes. The comparable values of the two different transfer reactions are explained by the values, determined in 1991 for three alkane solutes, of the cavity work and the solute-solvent interaction energy. The transfer free energy is the difference between the positive cavity work and the negative solute-solvent interaction energy. The interaction energy has similar values in water and liquid alkane that are intermediate in magnitude between the cavity work in water and in liquid alkane. These properties explain why the transfer free energy has comparable values (with opposite signs) in the two transfers. The current hydrophobic free energy is puzzling and poorly defined and needs a new definition and method of measurement. PMID:22529345

Solvatochromic probe behavior within choline chloride-based deep eutectic solvents: effect of temperature and water.

PubMed

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.

Micropolarity and Hydrogen-Bond Donor Ability of Environmentally Friendly Anionic Reverse Micelles Explored by UV/Vis Absorption of a Molecular Probe and FTIR Spectroscopy.

PubMed

Girardi, Valeria R; Silber, Juana J; Falcone, Ruben Darío; Correa, N Mariano

2018-03-19

In the present work we show how two biocompatible solvents, methyl laurate (ML) and isopropyl myristate (IPM), can be used as a less toxic alternative to replace the nonpolar component in a sodium 1,4-bis-2-ethylhexylsulfosuccinate (AOT) reverse micelles (RMs) formulation. In this sense, the micropolarity and the hydrogen-bond ability of the interface were monitored through the use of the solvatochromism of a molecular probe (1-methyl-8-oxyquinolinium betaine, QB) and Fourier transform infrared spectroscopy (FTIR). Our results demonstrate that the micropolarity sensed by QB in ML RMs is lower than in IPM RMs. Additionally, the water molecules form stronger H-bond interactions with the polar head of AOT in ML than in IPM. By FTIR was revealed that more water molecules interact with the interface in ML/AOT RMs. On the other hand, for AOT RMs generated in IPM, the weaker water-surfactant interaction allows the water molecules to establish hydrogen bonds with each other trending to bulk water more easily than in ML RMs, a consequence of the dissimilar penetration of nonpolar solvents into the interfacial region. The penetration process is strongly controlled by the polarity and viscosity of the external solvents. All of these results allow us to characterize these biocompatible systems, providing information about interfacial properties and how they can be altered by changing the external solvent. The ability of the nontoxic solvent to penetrate or not into the AOT interface produces a new interface with attractive properties. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

The Importance of Water for High Fidelity Information Processing and for Life

NASA Technical Reports Server (NTRS)

Hoehler, Tori M.; Pohorille, Andrew

2011-01-01

Is water an absolute prerequisite for life? Life depends on a variety of non-covalent interactions among molecules, the nature of which is determined as much by the solvent in which they occur as by the molecules themselves. Catalysis and information processing, two essential functions of life, require non-covalent molecular recognition with very high specificity. For example, to correctly reproduce a string consisting of 600,000 units of information (e.g ., 600 kilobases, equivalent to the genome of the smallest free living terrestrial organisms) with a 90% success rate requires specificity > 107 : 1 for the target molecule vs. incorrect alternatives. Such specificity requires (i) that the correct molecular association is energetically stabilized by at least 40 kJ/mol relative to alternatives, and (ii) that the system is able to sample among possible states (alternative molecular associations) rapidly enough to allow the system to fall under thermodynamic control and express the energetic stabilization. We argue that electrostatic interactions are required to confer the necessary energetic stabilization vs. a large library of molecular alternatives, and that a solvent with polarity and dielectric properties comparable to water is required for the system to sample among possible states and express thermodynamic control. Electrostatic associations can be made in non-polar solvents, but the resulting complexes are too stable to be "unmade" with sufficient frequency to confer thermodynamic control on the system. An electrostatic molecular complex representing 3 units of information (e.g., 3 base pairs) with specificity > 107 per unit has a stability in non-polar solvent comparable to that of a carbon-carbon bond at room temperature. These considerations suggest that water, or a solvent with properties very like water, is necessary to support high-fidelity information processing, and can therefore be considered a critical prerequisite for life.

Combinatorial Discovery of Cosolvent Systems for Production of Narrow Dispersion Thiolate-Protected Gold Nanoparticles

PubMed Central

2015-01-01

The effect of aqueous solvent concentration in the synthesis of water-soluble thiolate-protected gold nanoparticles (AuNPs) was investigated for 13 water-miscible solvents and three thiolate ligands (p-mercaptobenzoic acid, thiomalic acid, and glutathione). The results were analyzed by construction of heat maps that rank each reaction result for polydispersity. When solvents were organized in the heat map according to their Dimroth–Reichardt ET parameter (an approximate measure of polarity), two “hot spots” become apparent that are independent of the ligand used. We speculate that one hot spot may arise in part from the metal chelation or coordination ability of solvents that include diglyme, 1,2-dimethoxyethane, 1,4-dioxane, and tetrahydrofuran. The second hot spot arises at concentrations of alcohols including 2-propanol and 1-butanol that appear to selectively precipitate a growing product, presumably stopping its growth at a certain size. We observe some tightly dispersed products that appear novel. Overall, this study expands the number of tightly dispersed water-soluble AuNPs that can be directly synthesized. PMID:25459632

Combinatorial discovery of cosolvent systems for production of narrow dispersion thiolate-protected gold nanoparticles.

PubMed

Wong, O Andrea; Compel, W Scott; Ackerson, Christopher J

2015-01-12

The effect of aqueous solvent concentration in the synthesis of water-soluble thiolate-protected gold nanoparticles (AuNPs) was investigated for 13 water-miscible solvents and three thiolate ligands (p-mercaptobenzoic acid, thiomalic acid, and glutathione). The results were analyzed by construction of heat maps that rank each reaction result for polydispersity. When solvents were organized in the heat map according to their Dimroth-Reichardt ET parameter (an approximate measure of polarity), two "hot spots" become apparent that are independent of the ligand used. We speculate that one hot spot may arise in part from the metal chelation or coordination ability of solvents that include diglyme, 1,2-dimethoxyethane, 1,4-dioxane, and tetrahydrofuran. The second hot spot arises at concentrations of alcohols including 2-propanol and 1-butanol that appear to selectively precipitate a growing product, presumably stopping its growth at a certain size. We observe some tightly dispersed products that appear novel. Overall, this study expands the number of tightly dispersed water-soluble AuNPs that can be directly synthesized.

Exploration and characterization of new synthesis methods for C60 colloidal suspensions in water

NASA Astrophysics Data System (ADS)

Hilburn, Martha E.

Buckminsterfullerene, C60, has been used in the production of several commercial products from badminton racquets and lubricants for their mechanical properties to cosmetics and even dietary supplements for their "antioxidant" properties. Multi-ton production of C60 began in 2003 encouraging serious consideration of its fate in the environment in the case of an accidental release or improper disposal. Although C60 is practically insoluble in water, it readily forms stable aqueous colloidal suspensions (termed nC60) through solvent exchange methods or long-term vigorous stirring in water. Two new solvent exchange methods for synthesizing nC60 are presented. These methods combine key advantages of multiple existing synthesis methods including high yield, narrow particle size distribution, short synthesis time, and an absence of solvents such as tetrahydrofuran that have historically caused problems in laboratory synthesized aggregates. The resulting samples are attractive candidates for use in controlled environmental impact, biological, and toxicity studies. An improved method for quantifying residual solvents in nC60 samples utilizing solid phase micro extraction gas chromatography mass spectrometry (SPME-GC-MS) is also discussed.

Preferential solvation and solvation shell composition of free base and protonated 5, 10, 15, 20-tetrakis(4-sulfonatophenyl)porphyrin in aqueous organic mixed solvents

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.

Non-aqueous liquid compositions comprising ion exchange polymers reference to related application

DOEpatents

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.

The Chemistry of Liquid Ammonia.

ERIC Educational Resources Information Center

Lagowski, J. J.

1978-01-01

The solvent and chemical properties of liquid ammonia are presented. In a certain sense, ammonia is a more versatile solvent than is water because of its ability to solubilize, without reaction, highly negative or reducing species. (Author/BB)

Diagnosing Abiotic Degradation

EPA Science Inventory

The abiotic degradation of chlorinated solvents in ground water can be difficult to diagnose. Under current practice, most of the “evidence” is negative; specifically the apparent disappearance of chlorinated solvents with an accumulation of vinyl chloride, ethane, ethylene, or ...

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.

Synergetic Effects of Alcohol/Water Mixing on the Catalytic Reductive Fractionation of Poplar Wood

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

Renders, Tom; Van den Bosch, Sander; Vangeel, Thijs

One of the foremost challenges in lignocellulose conversion encompasses the integration of effective lignin valorization in current carbohydrate-oriented biorefinery schemes. Catalytic reductive fractionation (CRF) of lignocellulose offers a technology to simultaneously produce lignin-derived platform chemicals and a carbohydrate-enriched pulp via the combined action of lignin solvolysis and metal-catalyzed hydrogenolysis. Herein, the solvent (composition) plays a crucial role. In this contribution, we study the influence of alcohol/water mixtures by processing poplar sawdust in varying MeOH/water and EtOH/water blends. The results show particular effects that strongly depend on the applied water concentration. Low water concentrations enhance the removal of lignin from themore » biomass, while the majority of the carbohydrates are left untouched (scenario A). Contrarily, high water concentrations favor the solubilization of both hemicellulose and lignin, resulting in a more pure cellulosic residue (scenario B). For both scenarios, an evaluation was made to determine the most optimal solvent composition, based on two earlier introduced empirical efficiency descriptors (denoted LFDE and LFFE). According to these measures, 30 (A) and 70 vol % water (B) showed to be the optimal balance for both MeOH/water and EtOH/water mixtures. This successful implementation of alcohol/water mixtures allows operation under milder processing conditions in comparison to pure alcohol solvents, which is advantageous from an industrial point of view.« less

Stability of coordination compounds of Ni2+ and Co2+ ions with succinic acid anion in water-ethanol solvents

NASA Astrophysics Data System (ADS)

Tukumova, N. V.; Dieu Thuan, Tran Thi; Usacheva, T. R.; Koryshev, N. E.; Sharnin, V. A.

2017-04-01

Stability constants of the coordination compounds of nickel(II) and cobalt(II) ions with succinic acid anion in water-ethanol solvents are determined via potentiometric titration at ionic strength of 0.1 and at T = 298.15 K. It is found that logβ values of monoligand complexes of these ions and succinic acid anions rise along with the content of ethanol in solution ( X EtOH = 0-0.7 mole fractions). Based on an analysis of the thermodynamic characteristics of the solvation of the reagents involved in complex formation, it is found that the increased stability of succinate complexes of nickel(II) and cobalt(II) ions in water-ethanol solvents is mainly determined by the weakening of the solvation of succinic acid anion (Y2-).

On the dynamics of water molecules at the protein solute interfaces.

PubMed

Bernini, A; Spiga, O; Ciutti, A; Chiellini, S; Menciassi, N; Venditti, V; Niccolai, N

2004-10-01

Proteins, with the large variety of chemical groups they present at their molecular surface, are a class of molecules which can be very informative on most of the possible solute-solvent interactions. Hen egg white lysozyme has been used as a probe to investigate the complex solvent dynamics occurring at the protein surface, by analysing the results obtained from Nuclear Magnetic Resonance, X-ray diffractometry and Molecular Dynamics simulations. A consistent overall picture for the dynamics of water molecules close to the protein is obtained, suggesting that a rapid exchange occurs, in a picosecond timescale, among all the possible hydration surface sites both in solution and the solid state, excluding the possibility that solvent molecules can form liquid-crystal-like supramolecular adducts, which have been proposed as a molecular basis of 'memory of water'.

Free energy landscape for glucose condensation reactions.

PubMed

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

2010-12-16

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

Water isotope effect on the thermostability of a polio viral RNA hairpin: A metadynamics study.

PubMed

Pathak, Arup K; Bandyopadhyay, Tusar

2017-04-28

Oral polio vaccine is considered to be the most thermolabile of all the common childhood vaccines. Despite heavy water (D 2 O) having been known for a long time to stabilise attenuated viral RNA against thermodegradation, the molecular underpinnings of its mechanism of action are still lacking. Whereas, understanding the basis of D 2 O action is an important step that might reform the way other thermolabile drugs are stored and could possibly minimize the cold chain problem. Here using a combination of parallel tempering and well-tempered metadynamics simulation in light water (H 2 O) and in D 2 O, we have fully described the free energy surface associated with the folding/unfolding of a RNA hairpin containing a non-canonical basepair motif, which is conserved within the 3'-untranslated region of poliovirus-like enteroviruses. Simulations reveal that in heavy water (D 2 O) there is a considerable increase of the stability of the folded basin as monitored through an intramolecular hydrogen bond (HB), size, shape, and flexibility of RNA structures. This translates into a higher melting temperature in D 2 O by 41 K when compared with light water (H 2 O). We have explored the hydration dynamics of the RNA, hydration shell around the RNA surface, and spatial dependence of RNA-solvent collective HB dynamics in the two water systems. Simulation in heavy water clearly showed that D 2 O strengthens the HB network in the solvent, lengthens inter-residue water-bridge lifetime, and weakens dynamical coupling of the hairpin to its solvation environment, which enhances the rigidity of solvent exposed sites of the native configurations. The results might suggest that like other added osmoprotectants, D 2 O can act as a thermostabilizer when used as a solvent.

Water isotope effect on the thermostability of a polio viral RNA hairpin: A metadynamics study

NASA Astrophysics Data System (ADS)

Pathak, Arup K.; Bandyopadhyay, Tusar

2017-04-01

Oral polio vaccine is considered to be the most thermolabile of all the common childhood vaccines. Despite heavy water (D2O) having been known for a long time to stabilise attenuated viral RNA against thermodegradation, the molecular underpinnings of its mechanism of action are still lacking. Whereas, understanding the basis of D2O action is an important step that might reform the way other thermolabile drugs are stored and could possibly minimize the cold chain problem. Here using a combination of parallel tempering and well-tempered metadynamics simulation in light water (H2O) and in D2O, we have fully described the free energy surface associated with the folding/unfolding of a RNA hairpin containing a non-canonical basepair motif, which is conserved within the 3'-untranslated region of poliovirus-like enteroviruses. Simulations reveal that in heavy water (D2O) there is a considerable increase of the stability of the folded basin as monitored through an intramolecular hydrogen bond (HB), size, shape, and flexibility of RNA structures. This translates into a higher melting temperature in D2O by 41 K when compared with light water (H2O). We have explored the hydration dynamics of the RNA, hydration shell around the RNA surface, and spatial dependence of RNA-solvent collective HB dynamics in the two water systems. Simulation in heavy water clearly showed that D2O strengthens the HB network in the solvent, lengthens inter-residue water-bridge lifetime, and weakens dynamical coupling of the hairpin to its solvation environment, which enhances the rigidity of solvent exposed sites of the native configurations. The results might suggest that like other added osmoprotectants, D2O can act as a thermostabilizer when used as a solvent.

Development and evaluation of a gas chromatographic method for the determination of triazine herbicides in natural water samples

USGS Publications Warehouse

Steinheimer, T.R.; Brooks, M.G.

1984-01-01

A multi-residue method is described for the determination of triazine herbicides in natural water samples. The technique uses solvent extraction followed by gas chromatographic separation and detection employing nitrogen-selective devices. Seven compounds can be determined simultaneously at a nominal detection limit of 0.1 ??g/L in a 1-litre sample. Three different natural water samples were used for error analysis via evaluation of recovery efficiencies and estimation of overall method precision. As an alternative to liquid-liquid partition (solvent extraction) for removal of compounds of interest from water, solid-phase extraction (SPE) techniques employing chromatographic grade silicas with chemically modified surfaces have been examined. SPE is found to provide rapid and efficient concentration with quantitative recovery of some triazine herbicides from natural water samples. Concentration factors of 500 to 1000 times are obtained readily by the SPE technique.A multi-residue method is described for the determination of triazine herbicides in natural water samples. The technique uses solvent extraction followed by gas chromatographic separation and detection employing nitrogen-selective devices. Seven compounds can be determined simultaneously at a nominal detection limit of 0. 1 mu g/L in a 1-litre sample. As an alternative to liquid-liquid partition (solvent extraction) for removal of compounds of interest from water, solid-phase extraction (SPE) techniques employing chromatographic grade silicas with chemically modified surfaces have been examined. SPE is found to provide rapid and efficient concentration with quantitative recovery of some triazine herbicides from natural water samples. Concentration factors of 500 to 1000 times are obtained readily by the SPE technique.

Bioavailability of organic solvents in soils: Input into biologically based dose-response models for human risk assessments. 1998 annual progress report

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

Wester, R.C.; Maibach, H.I.

1998-06-01

'The purpose of this study is to determine the bioavailability of organic solvents following dermal exposures to contaminated soil and water. Breath analysis is being used to obtain real-time measurements of volatile organics in expired air following exposure in rats and humans. Rhesus monkeys will be used as surrogates for humans in benzene exposures. The exhaled breath data is being analyzed using physiologically based pharmacokinetic (PBPK) models to determine the dermal bioavailability of organic solvents under realistic exposure conditions. The end product of this research will be a tested framework for the rapid screening of real and potential exposures whilemore » simultaneously developing physiologically based pharmacokinetic (PBPK) models to comprehensively evaluate and compare exposures to organics from either contaminated soil or water. This report summarizes work 7 months into a 3-year project. Method development has produced systems for solvent exposure from soil and water which mimic actual exposure, and for which animals and human volunteers can be safely tested. Soil exposure is generally open to the air (working the soil) while water exposure is generally immersion. For 6--8 hour test exposure, a patch has been developed where soil is contained against the skin by a non-occlusive membrane, while simultaneously allowing volatilization of test solvent to the environment (activated charcoal). The water counterpart is an occlusive glass culture dish, sealed to skin with silicone adhesive. Shorter term exposure is done by one hand immersion in a bucket containing circulating water or soil, the volunteer instructed to move fingers through the water or soil. Human volunteers and animals breathe fresh air via a new breath-inlet system that allows for continuous real-time analysis of undiluted exhaled air. The air supply system is self-contained and separated from the exposure solvent-laden environment. The system uses a Teledyne 3DQ Discovery ion trap mass spectrometer (MS/MS) equipped with an atmospheric sampling glow discharge ionization source (ASGDI). The MS/MS system provides an appraisal of individual chemical components in the breath stream in the single-digit parts-per-billion (ppb) detectable range for each of the compounds proposed for study, while maintaining linearity of response over a wide dynamic range.'« less

Parametrization of Backbone Flexibility in a Coarse-Grained Force Field for Proteins (COFFDROP) Derived from All-Atom Explicit-Solvent Molecular Dynamics Simulations of All Possible Two-Residue Peptides.

PubMed

Frembgen-Kesner, Tamara; Andrews, Casey T; Li, Shuxiang; Ngo, Nguyet Anh; Shubert, Scott A; Jain, Aakash; Olayiwola, Oluwatoni J; Weishaar, Mitch R; Elcock, Adrian H

2015-05-12

Recently, we reported the parametrization of a set of coarse-grained (CG) nonbonded potential functions, derived from all-atom explicit-solvent molecular dynamics (MD) simulations of amino acid pairs and designed for use in (implicit-solvent) Brownian dynamics (BD) simulations of proteins; this force field was named COFFDROP (COarse-grained Force Field for Dynamic Representations Of Proteins). Here, we describe the extension of COFFDROP to include bonded backbone terms derived from fitting to results of explicit-solvent MD simulations of all possible two-residue peptides containing the 20 standard amino acids, with histidine modeled in both its protonated and neutral forms. The iterative Boltzmann inversion (IBI) method was used to optimize new CG potential functions for backbone-related terms by attempting to reproduce angle, dihedral, and distance probability distributions generated by the MD simulations. In a simple test of the transferability of the extended force field, the angle, dihedral, and distance probability distributions obtained from BD simulations of 56 three-residue peptides were compared to results from corresponding explicit-solvent MD simulations. In a more challenging test of the COFFDROP force field, it was used to simulate eight intrinsically disordered proteins and was shown to quite accurately reproduce the experimental hydrodynamic radii (Rhydro), provided that the favorable nonbonded interactions of the force field were uniformly scaled downward in magnitude. Overall, the results indicate that the COFFDROP force field is likely to find use in modeling the conformational behavior of intrinsically disordered proteins and multidomain proteins connected by flexible linkers.

Potential-specific structure at the hematite-electrolyte interface

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

McBriarty, Martin E.; Stubbs, Joanne; Eng, Peter

The atomic-scale structure of interfaces between metal oxides and aqueous electrolytes controls their catalytic, geochemical, and corrosion behavior. Measurements that probe these interfaces in situ provide important details of ion and solvent arrangements, but atomically precise structural models do not exist for common oxide-electrolyte interfaces far from equilibrium. Using a novel cell, we measured the structure of the hematite (a-Fe 2O 3) (110more » $$\\bar{2}$$)-electrolyte interface under controlled electrochemical bias using synchrotron crystal truncation rod X ray scattering. At increasingly cathodic potentials, charge-compensating protonation of surface oxygen groups increases the coverage of specifically bound water while adjacent water layers displace outwardly and became disordered. Returning to open circuit potential leaves the surface in a persistent metastable protonation state. The flux of current and ions at applied potential is thus regulated by a unique interfacial electrolyte environment, suggesting that electrical double layer models should be adapted to the dynamically changing interfacial structure far from equilibrium.« less

Application of enzyme-linked immunosorbent assay for measurement of polychlorinated biphenyls from hydrophobic solutions: Extracts of fish and dialysates of semipermeable membrane devices: Chapter 26

USGS Publications Warehouse

Zajicek, James L.; Tillitt, Donald E.; Huckins, James N.; Petty, Jimmie D.; Potts, Michael E.; Nardone, David A.

1996-01-01

Determination of PCBs in biological tissue extracts by enzyme-linked immunosorbent assays (ELISAs) can be problematic, since the hydrophobic solvents used for their extraction and isolation from interfering biochemicals have limited compatibility with the polar solvents (e.g. methanol/water) and the immunochemical reagents used in ELISA. Our studies of these solvent effects indicate that significant errors can occur when microliter volumes of PCB containing extracts, in hydrophobic solvents, are diluted directly into methanol/water diluents. Errors include low recovery and excess variability among sub-samples taken from the same sample dilution. These errors are associated with inhomogeneity of the dilution, which is readily visualized by the use of a hydrophobic dye, Solvent Blue 35. Solvent Blue 35 is also used to visualize the evaporative removal of hydrophobic solvent and the dissolution of the resulting PCB/dye residue by pure methanol and 50% (v/v) methanol/water, typical ELISA diluents. Evaporative removal of isooctane by an ambient temperature nitrogen purge with subsequent dissolution in 100% methanol gives near quantitative recovery of model PCB congeners. We also compare concentrations of total PCBs from ELISA (ePCB) to their corresponding concentrations determined from capillary gas chromatography (GC) in selected fish sample extracts and dialysates of semipermeable membrane device (SPMD) passive samplers using an optimized solvent exchange procedure. Based on Aroclor 1254 calibrations, ePCBs (ng/mL) determined in fish extracts are positively correlated with total PCB concentrations (ng/mL) determined by GC: ePCB = 1.16 * total-cPCB - 5.92. Measured ePCBs (ng/3 SPMDs) were also positively correlated (r2 = 0.999) with PCB totals (ng/3 SPMDs) measured by GC for dialysates of SPMDs: ePCB = 1.52 * total PCB - 212. Therefore, this ELISA system for PCBs can be a rapid alternative to traditional GC analyses for determination of PCBs in extracts of biota or in SPMD dialysates.

Brushless Cleaning of Solar Panels and Windows

NASA Technical Reports Server (NTRS)

Schneider, H. W.

1982-01-01

Machine proposed for cleaning solar panels and reflectors uses multiple vortexes of air, solvent, and water to remove dust and dirt. Uses no brushes that might abrade solar surfaces and thereby reduce efficiency. Machine can be readily automated and can be used on curved surfaces such as aparbolic reflectors as well as on flat ones. Cleaning fluids are recycled, so that large quantities of water and solvent are not needed.

Electro-driven extraction of inorganic anions from water samples and water miscible organic solvents and analysis by ion chromatography.

PubMed

Nojavan, Saeed; Bidarmanesh, Tina; Memarzadeh, Farkhondeh; Chalavi, Soheila

2014-09-01

A simple electromembrane extraction (EME) procedure combined with ion chromatography (IC) was developed to quantify inorganic anions in different pure water samples and water miscible organic solvents. The parameters affecting extraction performance, such as supported liquid membrane (SLM) solvent, extraction time, pH of donor and acceptor solutions, and extraction voltage were optimized. The optimized EME conditions were as follows: 1-heptanol was used as the SLM solvent, the extraction time was 10 min, pHs of the acceptor and donor solutions were 10 and 7, respectively, and the extraction voltage was 15 V. The mobile phase used for IC was a combination of 1.8 mM sodium carbonate and 1.7 mM sodium bicarbonate. Under these optimized conditions, all anions had enrichment factors ranging from 67 to 117 with RSDs between 7.3 and 13.5% (n = 5). Good linearity values ranging from 2 to 1200 ng/mL with coefficients of determination (R(2) ) between 0.987 and 0.999 were obtained. The LODs of the EME-IC method ranged from 0.6 to 7.5 ng/mL. The developed method was applied to different samples to evaluate the feasibility of the method for real applications. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Liquid eutectic GaIn as an alternative electrode for PTB7:PCBM organic solar cells

NASA Astrophysics Data System (ADS)

Thanh Hau Pham, Viet; Kieu Trinh, Thanh; Tam Nguyen Truong, Nguyen; Park, Chinho

2017-04-01

Conventional vacuum deposition process of aluminum (Al) is costly, time-consuming and difficult to apply to the large-scale production of organic photovoltaic devices (OPV). This paper reports a vacuum-free fabrication process of poly[[4,8-bis(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b‧]dithiophene-2,6-diyl][3-fluoro-2-[(2-ethylhexyl)carbonyl]thienophenediyl]:[6,6]-phenyl C71 butyric acid methyl ester (PTB7:PCBM) bulk heterojunction organic solar cell with liquid eutectic gallium-indium (EGaIn) electrode as an alternative to the common Al electrode. The insertion of a thin poly(ethylene oxide) (PEO) layer after depositing organic photoactive layer could help prevent the diffusion of liquid EGaIn into the active layer and allow the deposition of the EGaIn electrode. The PEO interfacial layer was formed by spin-coating from a mixed solvent of alcohol and water. Among different alcohol+water (methanol, ethanol, ethylene glycol, n-propanol, isopropanol, and isobutanol) mixed solvent tested, the n-propanol+water mixed solvent showed the greatest enhancement to the performance of OPVs. The improved device performance was attributed to the reactivity of mixed solvent n-propanol+water toward the surface of PTB7:PCBM active layer, which could help optimize surface morphology.

Hydrogen bonding donation of N-methylformamide with dimethylsulfoxide and water

NASA Astrophysics Data System (ADS)

Borges, Alexandre; Cordeiro, João M. M.

2013-04-01

20% N-methylformamide (NMF) mixtures with water and with dimethylsulfoxide (DMSO) have been studied. A comparison between the hydrogen bonding (H-bond) donation of N-methylformamide with both solvents in the mixtures is presented. Results of radial distribution functions, pair distribution energies, molecular dipole moment correlation, and geometry of the H-bonded species in each case are shown. The results indicate that the NMF - solvent H-bond is significantly stronger with DMSO than with water. The solvation shell is best organized in the DMSO mixture than in the aqueous one.

Method of removing and detoxifying a phosphorus-based substance

DOEpatents

Vandegrift, G.F.; Steindler, M.J.

1985-05-21

A method of removing a phosphorus-based poisonous substance from water contaminated is presented. In addition, the toxicity of the phosphorus-based substance is also subsequently destroyed. A water-immiscible organic solvent is first immobilized on a supported liquid membrane before the contaminated water is contacted with one side of the supported liquid membrane to absorb the phosphorus-based substance in the organic solvent. The other side of the supported liquid membrane is contacted with a hydroxy-affording strong base to react with phosphorus-based solvated species to form a non-toxic product.

[Extraction of lambda-cyhalothrin from aqueous dioxan solutions].

PubMed

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.

The Role of Interfacial Potential in Adsorbate Bonding: Electrode Potential-Dependent Infrared Spectra for Saturated CO Adlayers on Pt(110) and Related Electrochemical Surfaces in Varying Solvent Environments

DTIC Science & Technology

1992-05-01

as supporting electrolytes were recrystallized from methanol, water and ethanol , and water, respectively, and dried under vacuum at 110°C. Electrode...under these conditions 8,17 (vide infra). All measurements were performed at room temperature , 23±1*C. RESULTS AND DISCUSSION The experimental strategy...of interferometer scans during a suitably slow (2 mV s- ) positive-going potential sweep. For solvents containing traces of water, electrooxidative

The spatial range of protein hydration

NASA Astrophysics Data System (ADS)

Persson, Filip; Söderhjelm, Pär; Halle, Bertil

2018-06-01

Proteins interact with their aqueous surroundings, thereby modifying the physical properties of the solvent. The extent of this perturbation has been investigated by numerous methods in the past half-century, but a consensus has still not emerged regarding the spatial range of the perturbation. To a large extent, the disparate views found in the current literature can be traced to the lack of a rigorous definition of the perturbation range. Stating that a particular solvent property differs from its bulk value at a certain distance from the protein is not particularly helpful since such findings depend on the sensitivity and precision of the technique used to probe the system. What is needed is a well-defined decay length, an intrinsic property of the protein in a dilute aqueous solution, that specifies the length scale on which a given physical property approaches its bulk-water value. Based on molecular dynamics simulations of four small globular proteins, we present such an analysis of the structural and dynamic properties of the hydrogen-bonded solvent network. The results demonstrate unequivocally that the solvent perturbation is short-ranged, with all investigated properties having exponential decay lengths of less than one hydration shell. The short range of the perturbation is a consequence of the high energy density of bulk water, rendering this solvent highly resistant to structural perturbations. The electric field from the protein, which under certain conditions can be long-ranged, induces a weak alignment of water dipoles, which, however, is merely the linear dielectric response of bulk water and, therefore, should not be thought of as a structural perturbation. By decomposing the first hydration shell into polarity-based subsets, we find that the hydration structure of the nonpolar parts of the protein surface is similar to that of small nonpolar solutes. For all four examined proteins, the mean number of water-water hydrogen bonds in the nonpolar subset is within 1% of the value in bulk water, suggesting that the fragmentation and topography of the nonpolar protein-water interface has evolved to minimize the propensity for protein aggregation by reducing the unfavorable free energy of hydrophobic hydration.

Dynamical discrete/continuum linear response shells theory of solvation: convergence test for NH4+ and OH- ions in water solution using DFT and DFTB methods.

PubMed

de Lima, Guilherme Ferreira; Duarte, Hélio Anderson; Pliego, Josefredo R

2010-12-09

A new dynamical discrete/continuum solvation model was tested for NH(4)(+) and OH(-) ions in water solvent. The method is similar to continuum solvation models in a sense that the linear response approximation is used. However, different from pure continuum models, explicit solvent molecules are included in the inner shell, which allows adequate treatment of specific solute-solvent interactions present in the first solvation shell, the main drawback of continuum models. Molecular dynamics calculations coupled with SCC-DFTB method are used to generate the configurations of the solute in a box with 64 water molecules, while the interaction energies are calculated at the DFT level. We have tested the convergence of the method using a variable number of explicit water molecules and it was found that even a small number of waters (as low as 14) are able to produce converged values. Our results also point out that the Born model, often used for long-range correction, is not reliable and our method should be applied for more accurate calculations.

Distinct dissociation kinetics between ion pairs: Solvent-coordinate free-energy landscape analysis.

PubMed

Yonetani, Yoshiteru

2015-07-28

Different ion pairs exhibit different dissociation kinetics; however, while the nature of this process is vital for understanding various molecular systems, the underlying mechanism remains unclear. In this study, to examine the origin of different kinetic rate constants for this process, molecular dynamics simulations were conducted for LiCl, NaCl, KCl, and CsCl in water. The results showed substantial differences in dissociation rate constant, following the trend kLiCl < kNaCl < kKCl < kCsCl. Analysis of the free-energy landscape with a solvent reaction coordinate and subsequent rate component analysis showed that the differences in these rate constants arose predominantly from the variation in solvent-state distribution between the ion pairs. The formation of a water-bridging configuration, in which the water molecule binds to an anion and a cation simultaneously, was identified as a key step in this process: water-bridge formation lowers the related dissociation free-energy barrier, thereby increasing the probability of ion-pair dissociation. Consequently, a higher probability of water-bridge formation leads to a higher ion-pair dissociation rate.

Direct numerical solution of the Ornstein-Zernike integral equation and spatial distribution of water around hydrophobic molecules

NASA Astrophysics Data System (ADS)

Ikeguchi, Mitsunori; Doi, Junta

1995-09-01

The Ornstein-Zernike integral equation (OZ equation) has been used to evaluate the distribution function of solvents around solutes, but its numerical solution is difficult for molecules with a complicated shape. This paper proposes a numerical method to directly solve the OZ equation by introducing the 3D lattice. The method employs no approximation the reference interaction site model (RISM) equation employed. The method enables one to obtain the spatial distribution of spherical solvents around solutes with an arbitrary shape. Numerical accuracy is sufficient when the grid-spacing is less than 0.5 Å for solvent water. The spatial water distribution around a propane molecule is demonstrated as an example of a nonspherical hydrophobic molecule using iso-value surfaces. The water model proposed by Pratt and Chandler is used. The distribution agrees with the molecular dynamics simulation. The distribution increases offshore molecular concavities. The spatial distribution of water around 5α-cholest-2-ene (C27H46) is visualized using computer graphics techniques and a similar trend is observed.

Glasslike dynamical behavior of the plastocyanin hydration water

NASA Astrophysics Data System (ADS)

Bizzarri, Anna Rita; Paciaroni, Alessandro; Cannistraro, Salvatore

2000-09-01

The dynamical behavior of water around plastocyanin has been investigated in a wide temperature range by molecular dynamics simulation. The mean square displacements of water oxygen atoms show, at long times, a tα trend for all temperatures. Below 150 K, α is constant and equal to 1; at higher temperatures it drops to a value significantly smaller than 1, and thereafter decreases with increasing temperature. The occurrence of such an anomalous diffusion matches the onset of the dynamical transition observed in the protein. The intermediate scattering function of water is characterized, at high temperature, by a stretched exponential decay evolving, at low temperature, toward a two step relaxation behavior, which becomes more evident on increasing the exchanged wave vector q. Both the mean square displacements and the intermediate scattering functions show, beyond the ballistic regime, a plateau, which progressively extends for longer times as long as the temperature is lowered, such behavior reflecting trapping of water molecules within a cage formed by the nearest neighbors. At low temperature, a low frequency broad inelastic peak is observed in the dynamical structure factor of hydration water; such an excess of vibrational modes being reminiscent of the boson peak, characteristic of disordered, amorphous systems. All these features, which are typical of complex systems, can be traced back to the glassy character of the hydration water and suggest a dynamical coupling occurring at the macromolecule-solvent interface.

Effect of solvent type and high pressure treatment on the extraction of Gomphrena globosa L. bioactive compounds

NASA Astrophysics Data System (ADS)

Fernandes, L.; Ramalhosa, E.; Pereira, J. A.; Casal, S.; Saraiva, J. A.

2017-10-01

The present study aimed to compare the influence of different extraction solvents (water, methanol, water:acetone (6:4, v/v)), methods (heating (37 °C, 30 min) or high pressure (HP) (300 or 500 MPa) and extraction time (7.5 or 15 min)) on flavonoids, hydrolysable tannins and antioxidant activity (Total Reducing Capacity (TRC), DPPH Free Radical Scavenging Activity and Reducing Power) of Gomphrena globosa L. flower extracts. The water:acetone extracts obtained by heating had the highest values of flavonoids, hydrolysable tannins and antioxidant activity. When applying HP, variable results were obtained. Still, the application of HP to water allowed to extract more hydrolysable tannins, as well as to obtain extracts with higher antioxidant activity than with heating, but no significant alterations were observed with methanol. In conclusion, both solvent and extraction method influence the content of bioactive compounds, being HP treatment a promising method to obtain enriched aqueous extracts in line with the principles of green-chemistry.

Stoichiometric sensing to opt between gelation and crystallization.

PubMed

Vidyasagar, Adiyala; Sureshan, Kana M

2015-10-05

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

Cosolvent pretreatment in cellulosic biofuel production: Effect of tetrahydrofuran-water on lignin structure and dynamics

DOE PAGES

Smith, Micholas Dean; Mostofian, Barmak; Cheng, Xiaolin; ...

2015-10-05

The deconstruction of cellulose is an essential step in the production of ethanol from lignocellulosic biomass. However, the presence of lignin hinders this process. Recently, a novel cosolvent based biomass pretreatment method called CELF (Cosolvent Enhanced Lignocellulosic Fractionation) which employs tetrahydrofuran (THF) in a single phase mixture with water, was found to be highly effective at solubilizing and extracting lignin from lignocellulosic biomass and achieving high yields of fermentable sugars. Here, using all-atom molecular-dynamics simulation, we find that THF preferentially solvates lignin, and in doing so, shifts the equilibrium configurational distribution of the biopolymer from a crumpled globule to coil,more » independent of temperature. Whereas pure water is a bad solvent for lignin, the THF : water cosolvent acts as a "theta" solvent, in which solvent : lignin and lignin : lignin interactions are approximately equivalent in strength. Furthermore, under these conditions, polymers do not aggregate, thus providing a mechanism for the observed lignin solubilization that facilitates unfettered access of celluloytic enzymes to cellulose.« less

Multilevel Quantum Mechanics Theories and Molecular Mechanics Calculations of the Cl- + CH3I Reaction in Water.

PubMed

Liu, Peng; Li, Chen; Wang, Dunyou

2017-10-19

The Cl - + CH 3 I → CH 3 Cl + I - reaction in water was studied using combined multilevel quantum mechanism theories and molecular mechanics with an explicit water solvent model. The study shows a significant influence of aqueous solution on the structures of the stationary points along the reaction pathway. A detailed, atomic-level evolution of the reaction mechanism shows a concerted one-bond-broken and one-bond-formed mechanism, as well as a synchronized charge-transfer process. The potentials of mean force calculated with the CCSD(T) and DFT treatments of the solute produce a free activation barrier at 24.5 and 19.0 kcal/mol, respectively, which agrees with the experimental one at 22.0 kcal/mol. The solvent effects have also been quantitatively analyzed: in total, the solvent effects raise the activation energy by 20.2 kcal/mol, which shows a significant impact on this reaction in water.

SOLVENT - Simultaneous Observations of the Lunar Volatile EnvironmeNT

NASA Astrophysics Data System (ADS)

Livengood, T. A.; Anderson, C. M.; Chin, G.; Cohen, B.; Feaga, L.; Hewagama, T.; Protopapa, S.; Racette, P.

2018-02-01

SOLVENT will make Simultaneous Observations of the Lunar Volatile EnviornmeNT in complementary wavelength regimes, to measure the abundance of water and hydroxyl in the illuminated lunar surface and in the free space above it.

Method for recovering and using lignin in adhesive resins by extracting demethylated lignin

DOEpatents

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.

Extrusion of xylans extracted from corn cobs into biodegradable polymeric materials.

PubMed

Bahcegul, Erinc; Akinalan, Busra; Toraman, Hilal E; Erdemir, Duygu; Ozkan, Necati; Bakir, Ufuk

2013-12-01

Solvent casting technique, which comprises multiple energy demanding steps including the dissolution of a polymer in a solvent followed by the evaporation of the solvent from the polymer solution, is currently the main technique for the production of xylan based polymeric materials. The present study shows that sufficient water content renders arabinoglucuronoxylan (AGX) polymers extrudable, enabling the production of AGX based polymeric materials in a single step via extrusion, which is economically advantageous to solvent casting process for mass production. AGX polymers with water content of 27% were found to yield extrudates at an extrusion temperature of 90°C. The extruded strips showed very good mechanical properties with an ultimate tensile strength of 76 ± 6 MPa and elongation at break value of 35 ± 8%, which were superior to the mechanical properties of the strips obtained from polylactic acid. Copyright © 2013 Elsevier Ltd. All rights reserved.

Solvent screening for a hard-to-dissolve molecular crystal.

PubMed

Maiti, A; Pagoria, P F; Gash, A E; Han, T Y; Orme, C A; Gee, R H; Fried, L E

2008-09-01

Materials with a high-degree of inter- and intra-molecular hydrogen bonding generally have limited solubility in conventional organic solvents. This presents a problem for the dissolution, manipulation and purification of these materials. Using a state-of-the-art density-functional-theory based quantum chemical solvation model we systematically evaluated solvents for a known hydrogen-bonded molecular crystal. This, coupled with direct solubility measurements, uncovered a class of ionic liquids involving fluoride anions that possess more than two orders of magnitude higher solvation power as compared with the best conventional solvents. The crystal structure of one such ionic liquid, determined by X-ray diffraction spectroscopy, indicates that F- ions are stabilized through H-bonded chains with water. The presence of coordinating water in such ionic liquids seems to facilitate the dissolution process by keeping the chemical activity of the F- ions in check.

Molecular Dynamics Simulations of the Initial-State Predict Product Distributions of Dediazoniation of Aryldiazonium in Binary Solvents.

PubMed

Cruz, Gustavo N; Lima, Filipe S; Dias, Luís G; El Seoud, Omar A; Horinek, Dominik; Chaimovich, Hernan; Cuccovia, Iolanda M

2015-09-04

The dediazoniation of aryldiazonium salts in mixed solvents proceeds by a borderline SN1 and SN2 pathway, and product distribution should be proportional to the composition of the solvation shell of the carbon attached to the -N2 group (ipso carbon). The rates of dediazoniation of 2,4,6-trimethylbenzenediazonium in water, methanol, ethanol, propanol, and acetonitrile were similar, but measured product distributions were noticeably dependent on the nature of the water/cosolvent mixture. Here we demonstrated that solvent distribution in the first solvation shell of the ipso carbon, calculated from classical molecular dynamics simulations, is equal to the measured product distribution. Furthermore, we showed that regardless of the charge distribution of the initial state, i.e., whether the positive charge is smeared over the molecule or localized on phenyl moiety, the solvent distribution around the reaction center is nearly the same.

Analysis of polycyclic aromatic hydrocarbons in water and beverages using membrane-assisted solvent extraction in combination with large volume injection-gas chromatography-mass spectrometric detection.

PubMed

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.

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

PubMed

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

2016-03-14

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

Computing the Absorption and Emission Spectra of 5-Methylcytidine in Different Solvents: A Test-Case for Different Solvation Models.

PubMed

Martínez-Fernández, L; Pepino, A J; Segarra-Martí, J; Banyasz, A; Garavelli, M; Improta, R

2016-09-13

The optical spectra of 5-methylcytidine in three different solvents (tetrahydrofuran, acetonitrile, and water) is measured, showing that both the absorption and the emission maximum in water are significantly blue-shifted (0.08 eV). The absorption spectra are simulated based on CAM-B3LYP/TD-DFT calculations but including solvent effects with three different approaches: (i) a hybrid implicit/explicit full quantum mechanical approach, (ii) a mixed QM/MM static approach, and (iii) a QM/MM method exploiting the structures issuing from molecular dynamics classical simulations. Ab-initio Molecular dynamics simulations based on CAM-B3LYP functionals have also been performed. The adopted approaches all reproduce the main features of the experimental spectra, giving insights on the chemical-physical effects responsible for the solvent shifts in the spectra of 5-methylcytidine and providing the basis for discussing advantages and limitations of the adopted solvation models.

Method for recovering and using lignin in adhesive resins by extracting demethylated lignin

DOEpatents

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.

Method for recovering and using lignin in adhesive resins

DOEpatents

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.

Disaggregation induced solvatochromic switch: A study of dansylated polyglycerol dendrons in binary solvent mixture

NASA Astrophysics Data System (ADS)

Subuddhi, Usharani; Vuram, Prasanna K.; Chadha, Anju; Mishra, Ashok K.

2014-07-01

A reversal in solvatochromic behaviour was observed in second and third generation glycerol based dansylated polyether dendrons in water on addition of a second solvent like methanol or acetonitrile. Below a certain percentage of the nonaqueous solvent there is a negative-solvatochromism observed and above that there is a switch to positive-solvatochromism. The negative-solvatochromism is attributed to the progressive disaggregation of the dendron aggregates by the nonaqueous solvent component. Once the disaggregation process is complete, positive-solvatochromism is exhibited by the dendron monomers. Higher the hydrophobicity of the dendron more is the amount of the second solvent required for disaggregation.

Solvent Dependency in the Quantum Efficiency of 4-[(4-Aminophenyl)-(4-imino-1-cyclohexa-2, 5- dienylidene) methyl] Aniline Hydrochloride.

PubMed

Pathrose, Bini; Nampoori, V P N; Radhakrishnan, P; Sahira, H; Mujeeb, A

2015-05-01

In the present work dual beam thermal lens technique is used for studying the solvent dependency on the quantum efficiency of a novel dye used for biomedical applications. The role of solvent in the absolute fluorescence quantum yield of 4-[(4-Aminophenyl)-(4-imino-1-cyclohexa-2, 5- dienylidene) methyl] aniline hydrochloride is studied using thermal lens technique. It is observed that the variation in solvents and its concentration results considerable variations in the fluorescence quantum yield. These variations are due to the non-radiative relaxation of the absorbed energy and because of the different solvent properties. The highest quantum yield of the dye is observed in the polar protic solvent-water.

Organic solvent regeneration of granular activated carbon

NASA Astrophysics Data System (ADS)

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

1982-09-01

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

Application of finite inverse gas chromatography in hypromellose acetate succinate-water-acetone systems.

PubMed

Chiu, Sheng-Wei; Sturm, Derek R; Moser, Justin D; Danner, Ronald P

2016-09-30

A modification of a GC was developed to investigate both infinitely dilute and finite concentrations of solvents in polymers. Thermodynamic properties of hypromellose acetate succinate (HPMCAS-L)-acetone-water systems are important for the optimization of spray-drying processes used in pharmaceutical manufacturing of solid dispersion formulations. These properties, at temperatures below the glass transition temperature, were investigated using capillary column inverse gas chromatography (CCIGC). Water was much less soluble in the HPMCAS-L than acetone. Experiments were also conducted at infinitely dilute concentrations of one of the solvents in HPMCAS-L that was already saturated with the other solvent. Overall the partitioning of the water was not significantly affected by the presence of either water or acetone in the polymer. The acetone partition coefficient decreased as either acetone or water was added to the HPMCAS-L. A representation of the HPMCAS-L structure in terms of UNIFAC groups has been developed. With these groups, the UNIFAC-vdw-FV model did a reasonable job of predicting the phase equilibria in the binary and ternary systems. The Flory-Huggins correlation with fitted interaction parameters represented the data well. Copyright © 2016 Elsevier B.V. All rights reserved.

Peptide-based ambidextrous bifunctional gelator: applications in oil spill recovery and removal of toxic organic dyes for waste water management.

PubMed

Basu, Kingshuk; Nandi, Nibedita; Mondal, Biplab; Dehsorkhi, Ashkan; Hamley, Ian W; Banerjee, Arindam

2017-12-06

A low molecular weight peptide-based ambidextrous gelator molecule has been discovered for efficient control of water pollution. The gelator molecules can gel various organic solvents with diverse polarity, e.g. n -hexane, n -octane, petroleum ether, petrol, diesel, aromatic solvents like chlorobenzene, toluene, benzene, o -xylene and even aqueous phosphate buffer of pH 7.5. These gels have been thoroughly characterized using various techniques including field emission scanning electron microscopy, Fourier transform infrared spectroscopy, X-ray powder diffraction analysis, small angle X-ray scattering and rheological experiments. Interestingly, hydrogel obtained from the gelator molecule has been found to absorb toxic organic dyes (both cationic and anionic dyes) from dye-contaminated water. The gelator molecule can be reused for several cycles, indicating its possible future use in waste water management. Moreover, this gelator can selectively gel petrol, diesel, pump oil from an oil-water mixture in the presence of a carrier solvent, ethyl acetate, suggesting its efficient application for oil spill recovery. These results indicate that the peptide-based ambidextrous gelator produces soft materials (gels) with dual function: (i) removal of toxic organic dyes in waste water treatment and (ii) oil spill recovery.

A simple bubbling system for measuring radon (222Rn) gas concentrations in water samples based on the high solubility of radon in olive oil.

PubMed

Al-Azmi, D; Snopek, B; Sayed, A M; Domanski, T

2004-01-01

Based on the different levels of solubility of radon gas in organic solvents and water, a bubbling system has been developed to transfer radon gas, dissolving naturally in water samples, to an organic solvent, i.e. olive oil, which is known to be a good solvent of radon gas. The system features the application of a fixed volume of bubbling air by introducing a fixed volume of water into a flask mounted above the system, to displace an identical volume of air from an air cylinder. Thus a gravitational flow of water is provided without the need for pumping. Then, the flushing air (radon-enriched air) is directed through a vial containing olive oil, to achieve deposition of the radon gas by another bubbling process. Following this, the vial (containing olive oil) is measured by direct use of gamma ray spectrometry, without the need of any chemical or physical processing of the samples. Using a standard solution of 226Ra/222Rn, a lowest measurable concentration (LMC) of radon in water samples of 9.4 Bq L(-1) has been achieved (below the maximum contaminant level of 11 Bq L(-1)).

O2 and Water Migration Pathways between the Solvent and Heme Pockets of Hemoglobin with Open and Closed Conformations of the Distal HisE7.

PubMed

Shadrina, Maria S; Peslherbe, Gilles H; English, Ann M

2015-09-01

Hemoglobin transports O2 by binding the gas at its four hemes. Hydrogen bonding between the distal histidine (HisE7) and heme-bound O2 significantly increases the affinity of human hemoglobin (HbA) for this ligand. HisE7 is also proposed to regulate the release of O2 to the solvent via a transient E7 channel. To reveal the O2 escape routes controlled by HisE7 and to evaluate its role in gating heme access, we compare simulations of O2 diffusion from the distal heme pockets of the T and R states of HbA performed with HisE7 in its open (protonated) and closed (neutral) conformations. Irrespective of HisE7's conformation, we observe the same four or five escape routes leading directly from the α- or β-distal heme pockets to the solvent. Only 21-53% of O2 escapes occur via these routes, with the remainder escaping through routes that encompass multiple internal cavities in HbA. The conformation of the distal HisE7 controls the escape of O2 from the heme by altering the distal pocket architecture in a pH-dependent manner, not by gating the E7 channel. Removal of the HisE7 side chain in the GlyE7 variant exposes the distal pockets to the solvent, and the percentage of O2 escapes to the solvent directly from the α- or β-distal pockets of the mutant increases to 70-88%. In contrast to O2, the dominant water route from the bulk solvent is gated by HisE7 because protonation and opening of this residue dramatically increase the rate of influx of water into the empty distal heme pockets. The occupancy of the distal heme site by a water molecule, which functions as an additional nonprotein barrier to binding of the ligand to the heme, is also controlled by HisE7. Overall, analysis of gas and water diffusion routes in the subunits of HbA and its GlyE7 variant sheds light on the contribution of distal HisE7 in controlling polar and nonpolar ligand movement between the solvent and the hemes.

Solvent and substituent effects on aggregation constants of perylene bisimide π-stacks--a linear free energy relationship analysis.

PubMed

Chen, Zhijian; Fimmel, Benjamin; Würthner, Frank

2012-08-14

A series of six perylene bisimides (PBIs) with hydrophilic and hydrophobic side chains at the imide nitrogens were applied for a comparative study of the solvent and structural effects on the aggregation behaviour of this class of dyes. A comparison of the binding constants in tetrachloromethane at room temperature revealed the highest binding constant of about 10(5) M(-1) for a PBI bearing 3,4,5-tridodecyloxyphenyl substituents at the imide nitrogens, followed by 3,4,5-tridodecylphenyl and alkyl-substituted PBIs, whereas no aggregation could be observed in the accessible concentration range for PBIs equipped with bulky 2,6-diisopropylphenyl substituents at the imide nitrogens. The aggregation behaviour of three properly soluble compounds was investigated in 17 different solvents covering a broad polarity range from nonpolar n-hexane to highly polar DMSO and water. Linear free energy relationships (LFER) revealed a biphasic behaviour between Gibbs free energies of aggregation and common empirical solvent polarity scales indicating particularly strong π-π stacking interactions in nonpolar aliphatic and polar alcoholic solvents whilst the weakest binding is observed in dichloromethane and chloroform. Accordingly, PBI aggregation is dominated by electrostatic interactions in nonpolar solvents and by solvophobic interactions in protic solvents. In water, the aggregation constant is increased far beyond LFER expectations pointing at a pronounced hydrophobic effect.

Effective recovery of poly-β-hydroxybutyrate (PHB) biopolymer from Cupriavidus necator using a novel and environmentally friendly solvent system.

PubMed

Fei, Tao; Cazeneuve, Stacy; Wen, Zhiyou; Wu, Lei; Wang, Tong

2016-05-01

This work demonstrates a significant advance in bioprocessing for a high-melting lipid polymer. A novel and environmental friendly solvent mixture, acetone/ethanol/propylene carbonate (A/E/P, 1:1:1 v/v/v) was identified for extracting poly-hydroxybutyrate (PHB), a high-value biopolymer, from Cupriavidus necator. A set of solubility curves of PHB in various solvents was established. PHB recovery of 85% and purity of 92% were obtained from defatted dry biomass (DDB) using A/E/P. This solvent mixture is compatible with water, and from non-defatted wet biomass, PHB recovery of 83% and purity of 90% were achieved. Water and hexane were evaluated as anti-solvents to assist PHB precipitation, and hexane improved recovery of PHB from biomass to 92% and the purity to 93%. A scale-up extraction and separation reactor was designed, built and successfully tested. Properties of PHB recovered were not significantly affected by the extraction solvent and conditions, as shown by average molecular weight (1.4 × 10(6) ) and melting point (175.2°C) not being different from PHB extracted using chloroform. Therefore, this biorenewable solvent system was effective and versatile for extracting PHB biopolymers. © 2016 American Institute of Chemical Engineers Biotechnol. Prog., 32:678-685, 2016. © 2016 American Institute of Chemical Engineers.

Tailoring the Variational Implicit Solvent Method for New Challenges: Biomolecular Recognition and Assembly

PubMed Central

Ricci, Clarisse Gravina; Li, Bo; Cheng, Li-Tien; Dzubiella, Joachim; McCammon, J. Andrew

2018-01-01

Predicting solvation free energies and describing the complex water behavior that plays an important role in essentially all biological processes is a major challenge from the computational standpoint. While an atomistic, explicit description of the solvent can turn out to be too expensive in large biomolecular systems, most implicit solvent methods fail to capture “dewetting” effects and heterogeneous hydration by relying on a pre-established (i.e., guessed) solvation interface. Here we focus on the Variational Implicit Solvent Method, an implicit solvent method that adds water “plasticity” back to the picture by formulating the solvation free energy as a functional of all possible solvation interfaces. We survey VISM's applications to the problem of molecular recognition and report some of the most recent efforts to tailor VISM for more challenging scenarios, with the ultimate goal of including thermal fluctuations into the framework. The advances reported herein pave the way to make VISM a uniquely successful approach to characterize complex solvation properties in the recognition and binding of large-scale biomolecular complexes. PMID:29484300

Structure of block copolymer micelles in the presence of co-solvents

NASA Astrophysics Data System (ADS)

Robertson, Megan; Wang, Shu; Le, Kim Mai; Piemonte, Rachele; Madsen, Louis

2015-03-01

Amphiphilic block copolymer micelles in water are under broad exploration for drug delivery applications due to their high loading capacity and targeted drug delivery. We aim to understand the kinetic and thermodynamic processes that underlie the self-assembly of diblock copolymer micelle systems. The present work focuses on diblock copolymers containing poly(ethylene oxide) (a hydrophilic polymer) and polycaprolactone (a hydrophobic polymer), which spontaneously self-assemble into spherical micelles in water. Addition of a common good solvent (a co-solvent) for both of the constituting blocks, such as tetrahydrofuran (THF), reduces the interfacial tension at the core-corona interface. We are currently investigating the effect of this phenomenon on the micelle structural properties, using scattering experiments and nuclear magnetic resonance. We have characterized the hydrodynamic radius, core radius, corona thickness, aggregation number, degree of swelling of the micelle core with the co-solvent, and unimer (free chain) concentration, as a function of the co-solvent concentration. Fundamental knowledge from these studies will inform design of drug delivery systems by allowing us to tailor micelle properties for optimal cargo loading.

Characterization of naphthenic acids from athabasca oil sands using electrospray ionization: the significant influence of solvents.

PubMed

Headley, John V; Peru, Kerry M; Barrow, Mark P; Derrick, Peter J

2007-08-15

There is a need to develop routine and rugged methods for the characterization of oil sands naphthenic acids present in natural waters and contaminated soils. Mass spectra of naphthenic acids, obtained using a variant of electrospray ionization coupled with a Fourier transform ion cyclotron resonance mass spectrometer, are shown here to vary greatly, reflecting their dependence on solubilities of the acids in organic solvents. The solubilities of components in, for example, 1-octanol (similar solvent to fatty tissue) compared to polar solvents such as methanol or acetonitrile are used here as a surrogate to indicate the more bioavailable or toxic components of naphthenic acids in natural waters. Monocarboxylic compounds (CnH2n+zO2) in the z=-4, -6, and -12 (2-, 3-, and 6-ring naphthenic acids, respectively) family in the carbon number range of 13-19 were prevalent in all solvent systems. The surrogate method is intended to serve as a guide in the isolation of principle toxic components, which in turn supports efforts to remediate oil sands contaminated soils and groundwater.

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

PubMed

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

2017-07-28

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

Thermodynamic of cellulose solvation in novel solvent mixtures

NASA Astrophysics Data System (ADS)

Das, Ritankar; Chu, Jhih-Wei

2013-04-01

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

Thermodynamic of cellulose solvation in novel solvent mixtures

NASA Astrophysics Data System (ADS)

Das, Ritankar

2013-03-01

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

Thermodynamics of cellulose solvation in novel solvent mixtures

NASA Astrophysics Data System (ADS)

Das, Ritankar; Chu, Jhih-Wei

2012-10-01

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

Thermodynamic of cellulose solvation in novel solvent mixtures

NASA Astrophysics Data System (ADS)

Das, Ritankar

2012-11-01

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

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

DOEpatents

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

2007-03-27

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

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

DOEpatents

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

2004-06-22

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

Preparation of high-aspect-ratio ZnO nanorod arrays for the detection of several organic solvents at room working temperature

NASA Astrophysics Data System (ADS)

Lee, Yi-Mu; Zheng, Min-Ren

2013-11-01

Chemical sensors based on ZnO nanorod arrays were prepared using chemical bath deposition (CBD) to investigate the sensing performance for the detection of several organic solvents with low concentrations (0.1%, 0.5%, 1%, v/v) at room temperature. High quality and high aspect-ratio (value ˜28) ZnO nanorods have a diameter of about 74 nm and average length of 2.1 μm. Nyquist plots and Bode plots of the ZnO sensors under different organic solvents were obtained by electrical impedance spectroscopy (EIS). The sensing properties such as charge-transfer resistance, double-layer capacitance and dielectric parameters were determined from the impedance spectra to explore the charge transport in low-concentration aqueous solutions. The decreasing trend of the charge-transfer resistance (Rct) as decreasing solvent concentrations is observed, and a straight line at low frequency regime indicates adsorption of water molecules on the oxide surface. The sensitivity of the ZnO sensors was calculated from the resistance variation in target solvents and in deionized water. We demonstrated the use of ZnO nanorod arrays as a chemical sensor capable of generating a different response upon exposure to methanol, ethanol, isopropyl alcohol, acetone and water, wherein the methanol sensing exhibited highest sensitivity. In addition, the ZnO sensor also demonstrates good stability and reproducibility for detection of methanol and ethanol.

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.

MICROEMULSION OF MIXED CHLORINATED SOLVENTS USING FOOD GRADE (EDIBLE) SURFACTANTS

EPA Science Inventory

Ground water contamination frequently consists of mixed chlorinated solvents [e.g., tetrachloroethylene (PCE), trichloroethylene (TCE), and trans-1,2- dichloroethylene (DCE)]. In this research, mixtures of the food grade (edible) surfactants bis(2-ethylhexyl) sodium sulfosuccinat...

Switchable solvents and methods of use thereof

DOEpatents

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

2013-08-20

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

Switchable solvents and methods of use thereof

DOEpatents

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

2011-07-19

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

Switchable solvents and methods of use thereof

DOEpatents

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

2014-04-29

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

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

DOEpatents

Dumesic, James A.; Motagamwala, Ali Hussain

2017-06-27

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

Process for producing fuel grade ethanol by continuous fermentation, solvent extraction and alcohol separation

DOEpatents

Tedder, Daniel W.

1985-05-14

Alcohol substantially free of water is prepared by continuously fermenting a fermentable biomass feedstock in a fermentation unit, thereby forming an aqueous fermentation liquor containing alcohol and microorganisms. Continuously extracting a portion of alcohol from said fermentation liquor with an organic solvent system containing an extractant for said alcohol, thereby forming an alcohol-organic solvent extract phase and an aqueous raffinate. Said alcohol is separated from said alcohol-organic solvent phase. A raffinate comprising microorganisms and unextracted alcohol is returned to the fermentation unit.

Ionic association and solvation of the ionic liquid 1-hexyl-3-methylimidazolium chloride in molecular solvents revealed by vapor pressure osmometry, conductometry, volumetry, and acoustic measurements.

PubMed

Sadeghi, Rahmat; Ebrahimi, Nosaibah

2011-11-17

A systematic study of osmotic coefficient, conductivity, volumetric and acoustic properties of solutions of ionic liquid 1-hexyl-3-methylimidazolium chloride ([C(6)mim][Cl]) in various molecular solvents has been made at different temperatures in order to study of ionic association and solvation behavior of [C(6)mim][Cl] in different solutions. Precise measurements on electrical conductances of solutions of [C(6)mim][Cl] in water, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, and acetonitrile at 293.15, 298.15, and 303.15 K are reported and analyzed with Barthel's low-concentration chemical model (lcCM) to obtain the limiting molar conductivities and association constants of this ionic liquid in the investigated solvents. Strong ion pairing was found for the ionic liquid in 2-propanol, 1-butanol, and 1-propanol, whereas ion association in acetonitrile, methanol and ethanol is rather weak and in water the ionic liquid is fully dissociated. In the second part of this work, the apparent molar volumes and isentropic compressibilities of [C(6)mim][Cl] in water, methanol, ethanol, acetonitrile, 1-propanol, 2-propanol, and 1-butanol are obtained at the 288.15-313.15 K temperature range at 5 K intervals at atmospheric pressure from the precise measurements of density and sound velocity. The infinite dilution apparent molar volume and isentropic compressibility values of the free ions and ion pairs of [C(6)mim][Cl] in the investigated solvents as well as the excess molar volume of the investigated solutions are determined and their variations with temperature and type of solvents are also studied. Finally, the experimental measurements of osmotic coefficient at 318.15 K for binary solutions of [C(6)mim][Cl] in water, methanol, ethanol, 2-propanol, and acetonitrile are taken using the vapor pressure osmometry (VPO) method and from which the values of the solvent activity, vapor pressure, activity coefficients, and Gibbs free energies are calculated. The results are interpreted in terms of ion association, ion-dipole interactions, and structural factors of the ionic liquid and investigated organic solvents. The ionic liquid is solvated to a different extent by the molecular solvents, and ionic association is affected significantly by ionic solvation.

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

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

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

2013-02-01

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

Dependence of the enthalpies of formation of glycylglycinate complexes of nickel(II) on the composition of a mixed water-dimethylsulfoxide solvent

NASA Astrophysics Data System (ADS)

Naumov, V. V.; Kovaleva, Yu. A.; Isaeva, V. A.; Usacheva, T. R.; Sharnin, V. A.

2014-06-01

The heat effects of the complexation reactions of nickel(II) with a glycylglycinate ion in a water-dimethylsulfoxide solvent in a range of compositions of 0.00-0.60 molar parts of dimethylsulfoxide (DMSO) (an ionic strength of 0.1 was maintained using sodium perchlorate) were determined by means of calorimetry at 298.15 K. It is established that the exothermicity of complexation reactions rises by the first two steps and falls upon the addition of a third glycylglycinate anion with an increase in the concentration of DMSO. It is shown that the formation of mono- and bis-glycylglycinate complexes of nickel(II) in a water-DMSO solvent is determined mostly by the enthalpic contribution. It is concluded that the formation of tris-ligand complexes is more associated with the entropic contribution.

Solvation structures and dynamics of alkaline earth metal halides in supercritical water: A molecular dynamics study

NASA Astrophysics Data System (ADS)

Keshri, Sonanki; Mandal, Ratnamala; Tembe, B. L.

2016-09-01

Constrained molecular dynamics simulations of alkaline earth metal halides have been carried out to investigate their structural and dynamical properties in supercritical water. Potentials of mean force (PMFs) for all the alkaline earth metal halides in supercritical water have been computed. Contact ion pairs (CIPs) are found to be more stable than all other configurations of the ion pairs except for MgI2 where solvent shared ion pair (SShIP) is more stable than the CIP. There is hardly any difference in the PMFs between the M2+ (M = Mg, Ca, Sr, Ba) and the X- (X = F, Cl, Br, I) ions whether the second X- ion is present in the first coordination shell of the M2+ ion or not. The solvent molecules in the solvation shells diffuse at a much slower rate compared to the bulk. Orientational distribution functions of solvent molecules are sharper for smaller ions.

A surprising method for green extraction of essential oil from dry spices: Microwave dry-diffusion and gravity.

PubMed

Farhat, Asma; Fabiano-Tixier, Anne-Sylvie; Visinoni, Franco; Romdhane, Mehrez; Chemat, Farid

2010-11-19

Without adding any solvent or water, we proposed a novel and green approach for the extraction of secondary metabolites from dried plant materials. This "solvent, water and vapor free" approach based on a simple principle involves the application of microwave irradiation and earth gravity to extract the essential oil from dried caraway seeds. Microwave dry-diffusion and gravity (MDG) has been compared with a conventional technique, hydrodistillation (HD), for the extraction of essential oil from dried caraway seeds. Essential oils isolated by MDG were quantitatively (yield) and qualitatively (aromatic profile) similar to those obtained by HD, but MDG was better than HD in terms of rapidity (45min versus 300min), energy saving, and cleanliness. The present apparatus permits fast and efficient extraction, reduces waste, avoids water and solvent consumption, and allows substantial energy savings. Copyright © 2010 Elsevier B.V. All rights reserved.

Internal friction in an intrinsically disordered protein—Comparing Rouse-like models with experiments

NASA Astrophysics Data System (ADS)

Soranno, Andrea; Zosel, Franziska; Hofmann, Hagen

2018-03-01

Internal friction is frequently found in protein dynamics. Its molecular origin however is difficult to conceptualize. Even unfolded and intrinsically disordered polypeptide chains exhibit signs of internal friction despite their enormous solvent accessibility. Here, we compare four polymer theories of internal friction with experimental results on the intrinsically disordered protein ACTR (activator of thyroid hormone receptor). Using nanosecond fluorescence correlation spectroscopy combined with single-molecule Förster resonance energy transfer (smFRET), we determine the time scales of the diffusive chain dynamics of ACTR at different solvent viscosities and varying degrees of compaction. Despite pronounced differences between the theories, we find that all models can capture the experimental viscosity-dependence of the chain relaxation time. In contrast, the observed slowdown upon chain collapse of ACTR is not captured by any of the theories and a mechanistic link between chain dimension and internal friction is still missing, implying that the current theories are incomplete. In addition, a discrepancy between early results on homopolymer solutions and recent single-molecule experiments on unfolded and disordered proteins suggests that internal friction is likely to be a composite phenomenon caused by a variety of processes.

Internal friction in an intrinsically disordered protein-Comparing Rouse-like models with experiments.

PubMed

Soranno, Andrea; Zosel, Franziska; Hofmann, Hagen

2018-03-28

Internal friction is frequently found in protein dynamics. Its molecular origin however is difficult to conceptualize. Even unfolded and intrinsically disordered polypeptide chains exhibit signs of internal friction despite their enormous solvent accessibility. Here, we compare four polymer theories of internal friction with experimental results on the intrinsically disordered protein ACTR (activator of thyroid hormone receptor). Using nanosecond fluorescence correlation spectroscopy combined with single-molecule Förster resonance energy transfer (smFRET), we determine the time scales of the diffusive chain dynamics of ACTR at different solvent viscosities and varying degrees of compaction. Despite pronounced differences between the theories, we find that all models can capture the experimental viscosity-dependence of the chain relaxation time. In contrast, the observed slowdown upon chain collapse of ACTR is not captured by any of the theories and a mechanistic link between chain dimension and internal friction is still missing, implying that the current theories are incomplete. In addition, a discrepancy between early results on homopolymer solutions and recent single-molecule experiments on unfolded and disordered proteins suggests that internal friction is likely to be a composite phenomenon caused by a variety of processes.

Uranyl extraction by N,N-dialkylamide ligands studied using static and dynamic DFT simulations.

PubMed

Sieffert, Nicolas; Wipff, Georges

2015-02-14

We report DFT static and dynamic studies on uranyl complexes [UO(2)(NO(3))x(H(2)O)(y)L(z)](2-x) involved in the uranyl extraction from water to an "oil" phase (hexane) by an amide ligand L (N,N-dimethylacetamide). Static DFT results "in solution" (continuum SMD models for water and hexane) predict that the stepwise formation of [UO(2)(NO(3))(2)L(2)] from the UO(2)(H(2)O)(5)(2+) species is energetically favourable, and allow us to compare cis/trans isomers of penta- and hexa-coordinated complexes and key intermediates in the two solvents. DFT-MD simulations of [UO(2)(NO(3))(2)L(2)], [UO(2)(NO(3))(2)(H(2)O)L(2)], and [UO(2)(NO(3))(H(2)O)L(2)](+) species in explicit solvent environments (water, hexane, or the water/hexane interface) represented at the MM or full-DFT level reveal a versatile solvent dependent binding mode of nitrates, also evidenced by metadynamics simulations. In water and at the interface, the latter exchange from bi- to monodentate, via in plane rotational motions in some cases. Remarkably, structures of complexes at the interface are more "water-like" than gas phase- or hexane-like. Thus, the order of U-O(NO(3))/U-O(L) bond distances observed in the gas phase (U-O(nit) < U-OL) is inverted at the interface and in water. Overall, the results are consistent with the experimental observation of uranyl extraction from nitric acid solutions by amide analogues (bearing "fatty" substituents), and allow us to propose possible extraction mechanisms, involving complexation of L "right at the interface". They also point to the importance of the solvent environment and the dynamics on the structure and stability of the complexes.

Water as a matrix for life

NASA Technical Reports Server (NTRS)

Pohorille, Andrew; Pratt, Lawrence

2006-01-01

"Follow the water" is the canonical strategy in searching for life in the universe. Conventionally, discussion of this topic is focused on how solvent supports organic chemistry sufficiently rich to seed life. Perhaps more importantly, solvent must promote self-organization of organic matter into functional structures capable of responding to environmental changes. This process is based on non-covalent interactions. They are constantly formed and broken in response to internal and external stimuli. This requires that their strength must be properly tuned. If they were too weak, the system would exhibit undesired, uncontrolled response to natural fluctuations of physical and chemical parameters. If they were too strong kinetics of biological processes would be slow and energetics costly. Non-covalent interactions are strongly mediated by the solvent. Specifically, high dielectric solvents for life are needed for solubility of polar species and flexibility of biological structures stabilized by electrostatic interactions. Water exhibits a remarkable trait that it promotes solvophobic interactions between non-polar species, which are responsible for self-organization phenomena such as the formation of cellular boundary structures, and protein folding and aggregation. Unusual temperature dependence of hydrophobic interactions - they often become stronger as temperature increases - is a consequence of the temperature insensitivity of properties of the liquid water. This contributes to the existence of robust life over a wide temperature range. Water is not the only liquid with favorable properties for supporting life. Other pure liquids or their mixtures that have high dielectric constants and simultaneously support some level of self-organization will be discussed.

Quantum Chemically Estimated Abraham Solute Parameters Using Multiple Solvent-Water Partition Coefficients and Molecular Polarizability.

PubMed

Liang, Yuzhen; Xiong, Ruichang; Sandler, Stanley I; Di Toro, Dominic M

2017-09-05

Polyparameter Linear Free Energy Relationships (pp-LFERs), also called Linear Solvation Energy Relationships (LSERs), are used to predict many environmentally significant properties of chemicals. A method is presented for computing the necessary chemical parameters, the Abraham parameters (AP), used by many pp-LFERs. It employs quantum chemical calculations and uses only the chemical's molecular structure. The method computes the Abraham E parameter using density functional theory computed molecular polarizability and the Clausius-Mossotti equation relating the index refraction to the molecular polarizability, estimates the Abraham V as the COSMO calculated molecular volume, and computes the remaining AP S, A, and B jointly with a multiple linear regression using sixty-five solvent-water partition coefficients computed using the quantum mechanical COSMO-SAC solvation model. These solute parameters, referred to as Quantum Chemically estimated Abraham Parameters (QCAP), are further adjusted by fitting to experimentally based APs using QCAP parameters as the independent variables so that they are compatible with existing Abraham pp-LFERs. QCAP and adjusted QCAP for 1827 neutral chemicals are included. For 24 solvent-water systems including octanol-water, predicted log solvent-water partition coefficients using adjusted QCAP have the smallest root-mean-square errors (RMSEs, 0.314-0.602) compared to predictions made using APs estimated using the molecular fragment based method ABSOLV (0.45-0.716). For munition and munition-like compounds, adjusted QCAP has much lower RMSE (0.860) than does ABSOLV (4.45) which essentially fails for these compounds.